WO2020031766A1

WO2020031766A1 - Method for manufacturing prepreg, coating device, and apparatus for manufacturing prepreg

Info

Publication number: WO2020031766A1
Application number: PCT/JP2019/029607
Authority: WO
Inventors: 越智隆志; 西野聡; 箕浦潔
Original assignee: 東レ株式会社
Priority date: 2018-08-09
Filing date: 2019-07-29
Publication date: 2020-02-13
Also published as: JPWO2020031766A1; US11639427B2; EP3835342A1; CN112533984B; US20210301096A1; US20230106616A1; EP3835342A4; US11421091B2; CN112533984A; JP6696630B1

Abstract

Regarding a method for manufacturing a prepreg by applying a matrix resin to a reinforcing fiber sheet, the present invention addresses the problem of providing a method for manufacturing a prepreg, wherein the prepreg can be continuously manufactured without clogging due to fluff generated during the manufacturing process, even when the prepreg is manufactured at high speed, and the reinforcing fiber sheet can be efficiently impregnated with the matrix resin. This method for manufacturing a prepreg comprises a step for applying a matrix resin 2 to a reinforcing fiber sheet by passing the reinforcing fiber sheet through a coating unit 20, in which the matrix resin 2 is stored, in a horizontal or inclined direction, wherein the coating unit 20 includes a liquid reservoir and a constriction in communication with each other, the liquid reservoir has a portion in which the cross-sectional area decreases continuously along the travel direction of the reinforcing fiber sheet, and the constriction has a slit-like cross section having a cross-sectional area smaller than the maximum cross-sectional area of the liquid reservoir.

Description

Prepreg manufacturing method, coating apparatus and prepreg manufacturing apparatus

The present invention relates to a method for producing a prepreg, and more particularly to a method for producing a prepreg by uniformly impregnating a reinforcing fiber sheet with a matrix resin.

Fiber reinforced composite material (FRP), which is a matrix resin containing thermoplastic resin and thermosetting resin reinforced with reinforcing fibers, is a material for aviation and space, automotive material, industrial material, pressure vessel, building material, housing, medical equipment. It is used in various fields such as applications and sports. Particularly when high mechanical properties and lightness are required, carbon fiber reinforced composite materials (CFRP) are widely and suitably used. On the other hand, when cost is prioritized over mechanical properties and light weight, a glass fiber reinforced composite material (GFRP) may be used. In the FRP, a reinforcing fiber bundle is impregnated with a matrix resin to obtain an intermediate base material, which is laminated and molded, and when a thermosetting resin is used, is thermoset to produce a member made of FRP. In the above-mentioned applications, there are many planar objects and those obtained by bending the same, and the two-dimensional sheet-like material is more often used as an intermediate substrate of FRP than a one-dimensional strand or roving-like material when producing a member. It is widely used from the viewpoint of lamination efficiency and moldability.

最近 In recent years, in order to improve the production efficiency of members made of FRP, mechanization and automation of lamination of sheet-like intermediate substrates have been promoted, and narrow-width tape-like intermediate substrates are preferably used here. The narrow tape-shaped intermediate substrate can be obtained by slicing a wide sheet-shaped intermediate substrate at a desired width, or by impregnating a narrow reinforcing fiber sheet directly with a matrix resin.

プリ Prepreg is generally used as a two-dimensional sheet-like intermediate substrate. The prepreg is prepared by applying and impregnating a matrix resin to a reinforcing fiber. Examples of the reinforcing fiber sheet include a unidirectional material (UD base material) in which a plurality of reinforcing fibers are arranged on a surface in one direction, a reinforcing fiber in which reinforcing fibers are arranged in a multiaxial manner, or a sheet formed by random arrangement. There is a fabric.

Hot-melt method, one of the prepreg manufacturing methods, is to melt the matrix resin, coat it on release paper, create a laminated structure sandwiched between the upper and lower surfaces of the reinforcing fiber sheet, and apply heat and pressure. The matrix resin is impregnated inside the reinforcing fiber sheet. This method has a problem that the number of steps is large, the production speed cannot be increased, and the cost is high.

提案 There has been a proposal for improving the efficiency of impregnation, for example, as in Patent Document 1. In this method, a glass fiber is melt-spun and then bundled into a strand or roving to pass through a liquid reservoir having a conical flow path filled with a thermoplastic resin.

On the other hand, a method for simultaneously forming a coating film on both sides of a sheet material is described in Patent Document 2. However, in order to prevent the fluctuation of the sheet material at the time of forming the coating film, the sheet material is passed through a web guide. After that, coating is performed with a pipe type doctor.

As a method for producing a strip-shaped prepreg using a thermoplastic resin, a strip-type reinforcing fiber bundle is conveyed in a horizontal direction (horizontal direction), passed through a die, and a thermoplastic resin is applied to and impregnated into the strip-shaped reinforcing fiber bundle. Patent document 3) is known. In Patent Document 3, a plurality of band-shaped reinforcing fiber bundles are separately introduced into a die filled with a molten thermoplastic resin, and are opened, impregnated, and laminated by a fixed guide (for example, a squeeze bar). It is described that the sheet-shaped prepreg is pulled out from a die.

Patent Document 4 describes an apparatus that fills a manifold with a thermoplastic resin and applies ultrasonic vibration to an outlet in a pultrusion method of vertically pulling out a reinforcing fiber bundle.

International Publication WO2001 / 028951 pamphlet JP-A-10-337516 International Publication WO2012 / 002417 pamphlet JP-A-1-178412

では The method of Patent Document 1 can only produce strands or rovings, and cannot be applied to the production of sheet prepregs that are the subject of the present invention. Further, in Patent Literature 1, in order to improve the impregnation efficiency, a fluid of a thermoplastic resin is applied to the strand or the side surface of the roving-like reinforcing fiber bundle to generate turbulent flow positively in the conical flow path. This is thought to be intended to partially disturb the arrangement of the reinforcing fiber bundle and allow the matrix resin to flow in.However, when this concept is applied to the reinforcing fiber sheet, the reinforcing fiber sheet is deformed, and the quality of the prepreg is reduced. It is thought that not only does the FRP decrease, but also the mechanical properties of the FRP decrease.

In addition, when the technique of Patent Document 2 is applied, it is considered that fluff is generated by rubbing with the web guide, and the running of the reinforcing fiber sheet becomes difficult. Further, the technique of Patent Document 2 is coating of a resin, and impregnation is not intended.

では In addition, in the method of Patent Document 3, fluff is likely to stay in the liquid pool during continuous production, and fluff is likely to be clogged in the withdrawn part. In particular, when the band-shaped reinforcing fiber bundle is continuously run at a high speed, the frequency of clogging of the fluff is extremely increased, so that production can be performed only at a very low speed, and there is a problem that productivity is not improved.

Further, in the method described in Patent Document 4, a nozzle portion not filled with resin is provided on the upper portion of the manifold, and the nozzle can be optimized with a strand or a roving-like material. It is difficult to cope with the shape, and when the reinforcing fiber sheet passes therethrough, fluff is generated, and when it is brought into the manifold, it is considered that it is likely to be clogged with a die.

Thus, an efficient method of applying a matrix resin to a reinforcing fiber sheet and an efficient method of producing a prepreg have not been established yet.

An object of the present invention is to reduce the generation of fluff in the prepreg production method, to enable continuous production without clogging of fluff, and to impregnate the reinforcing fiber sheet with a matrix resin efficiently, thereby increasing the production speed. An object of the present invention is to provide a prepreg manufacturing method and a coating apparatus that are possible.

The method for producing a prepreg according to the present invention that solves the above-mentioned problem provides a matrix resin to a reinforcing fiber sheet by passing a reinforcing fiber sheet in a horizontal direction or an inclined direction inside an application section in which a matrix resin is stored. A method of manufacturing a prepreg, comprising: a step of forming a prepreg, wherein the application section includes a liquid reservoir and a constriction that are communicated with each other, and the liquid reservoir has a continuously decreasing cross-sectional area along a running direction of a reinforcing fiber sheet. The constriction has a slit-shaped cross-section and has a cross-sectional area smaller than the maximum cross-sectional area of the liquid reservoir, and has a width L at the terminal end of the liquid reservoir, and an outlet at the constriction. The width W of the sheet-like reinforcing fiber bundle satisfies the relationship of the following formula (1).

{L ≦ W + 10 (mm)} (1)

Further, the coating device of the present invention is a coating device for applying a matrix resin to the reinforcing fiber sheet, and has a running mechanism for running the reinforcing fiber sheet in a horizontal direction or an inclined direction, and an application mechanism, The mechanism is capable of storing a matrix resin therein, and further includes a liquid reservoir and a constricted portion that are communicated with each other, and the liquid reservoir has a continuous cross-sectional area along the running direction of the reinforcing fiber sheet. It has a decreasing portion, and the constricted portion has a slit-shaped cross section and has a cross-sectional area smaller than the maximum cross-sectional area of the liquid reservoir.

Further, the prepreg manufacturing apparatus of the present invention is provided with a gantry for mounting reinforcing fibers or reinforced fiber fabrics, the coating apparatus, and a winder for winding up the prepreg.

According to the prepreg manufacturing method of the present invention, clogging due to fluff can be significantly suppressed and prevented. Further, the reinforced fiber sheet can be run continuously and at a high speed, and the productivity of the prepreg is improved.

1 is a schematic cross-sectional view showing a prepreg manufacturing method and a coating apparatus according to an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing a prepreg manufacturing method and a coating apparatus according to another embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing a prepreg manufacturing method and a coating apparatus according to another embodiment of the present invention. FIG. 4 is a schematic cross-sectional view showing a prepreg manufacturing method and a coating apparatus according to another embodiment of the present invention. FIG. 2 is a cross-sectional view illustrating a structure of an application unit outlet when the application unit 20 in FIG. 1 is viewed from a direction opposite to X in FIG. 1. FIG. 2 is a cross-sectional view illustrating a structure inside the application unit when the application unit 20 in FIG. 1 is viewed from a Z direction in FIG. 1. FIG. 7 is a cross-sectional view illustrating a flow of a matrix resin 2 in a gap 33 in FIG. 6. It is a figure showing an example of installation of a width regulation mechanism. FIG. 2 is a detailed cross-sectional view of the vicinity of an outlet of a coating unit 20 in the embodiment of FIG. FIG. 10 is a detailed cross-sectional view of the vicinity of an outlet of a coating unit 20b according to another embodiment different from FIG. 9. FIG. 10 is a detailed cross-sectional view of the vicinity of an outlet of a coating unit 20c according to another embodiment different from FIG. 9. FIG. 10 is a detailed cross-sectional view of the vicinity of an outlet of a coating unit 20d according to another embodiment different from FIG. 9. It is a detailed cross-sectional view near the exit of the application section 40 of an embodiment different from the present invention. FIG. 10 is a detailed cross-sectional view of a coating unit 20e according to another embodiment different from FIG. 9. It is the schematic which shows the example of the prepreg manufacturing process and apparatus using this invention. It is the schematic of an example of another prepreg manufacturing process and apparatus using this invention. It is the schematic of an example of another prepreg manufacturing process and apparatus using this invention. It is a figure showing the example of the mode provided with a plurality of application parts concerning one embodiment of the present invention. It is a figure showing the example of the mode of laminating a plurality of prepregs concerning one embodiment of the present invention. It is a figure showing the simulation result (hydraulic pressure) of H = 50. It is a figure which shows the simulation result (liquid flow) of H = 50. It is a figure showing the simulation result (fluid pressure) of H = 1. It is a figure which shows the simulation result (liquid flow) of H = 50. It is a figure showing a simulation result (fluid pressure) of H = 0. It is a figure showing the simulation result (liquid flow) of H = 0. It is a figure showing the simulation result (liquid flow, flow velocity) when H was changed. FIG. 10 is a detailed cross-sectional view of a coating unit 20f according to another embodiment different from FIG. 9. It is the schematic of an example of another prepreg manufacturing process and apparatus using this invention. FIG. 10 is a detailed cross-sectional view of a coating unit 20g according to another embodiment different from FIG. 9. It is the schematic of an example of another prepreg manufacturing process and apparatus using this invention. It is the schematic of an example of another prepreg manufacturing process and apparatus using this invention. FIG. 10 is a detailed cross-sectional view of an application unit 20h according to another embodiment different from FIG. 9.

望ましい Preferred embodiments of the present invention will be described with reference to the drawings. Note that the following description exemplifies embodiments of the present invention, and the present invention is not construed as being limited thereto, and various modifications can be made without departing from the objects and effects of the present invention. .

<Outline of prepreg manufacturing method>
First, the outline of the method for producing a prepreg of the present invention will be described with reference to FIG. FIG. 1 is a schematic sectional view showing a prepreg manufacturing method and apparatus according to one embodiment of the present invention. The coating device 100 is provided between the transport rolls 14 and 15, which are transport mechanisms for moving the reinforcing fiber sheet 1b in a horizontal direction or an inclined direction, and is provided between the transport rolls 14 and 15, and the coating in which the matrix resin 2 is stored. A unit 20 is provided. The matrix resin may have fluidity by itself, or may have fluidity by containing a solvent, a plasticizer, or the like. In addition, before and after the coating apparatus 100, a plurality of creels 11 for unwinding the reinforcing fibers 1a and a reinforcing fiber sheet 1b in which the unwound reinforcing fibers 1a are arranged in one direction (in FIG. 1, arranged in the depth direction of the paper). And a winding device 17 for the prepreg 1d. Although not shown, the coating device 100 is provided with a matrix resin amount monitoring means and a matrix resin supply device. (The same applies to other examples). Further, a supply device 16a for supplying the release sheet 3 and a supply device 16b for supplying the resin film 4 are provided.

<Reinforced fiber sheet>
Here, as the reinforcing fiber, carbon fiber, glass fiber, metal fiber, metal oxide fiber, metal nitride fiber, organic fiber (aramid fiber, polybenzoxazole fiber, polyvinyl alcohol fiber, polyethylene fiber, polyester fiber, polyamide fiber And the like, but the use of carbon fibers is preferable from the viewpoint of the mechanical properties and light weight of the FRP.

Examples of the reinforcing fiber sheet include a unidirectional material (UD base material) in which a plurality of reinforcing fibers are arranged on a surface in one direction, a reinforcing fiber in which reinforcing fibers are arranged in a multiaxial manner, or a sheet formed by random arrangement. Fabric.

方法 The method of forming the UD base material is not particularly limited, and may be formed using a known method. It is preferable to form a reinforcing fiber sheet in which single fibers are arranged in advance, and to further arrange the reinforcing fiber bundle to form a reinforcing fiber sheet from the viewpoint of process efficiency and uniform arrangement. For example, in the case of carbon fibers, a tow, which is a tape-like reinforcing fiber bundle, is wound around a bobbin, and a reinforcing fiber sheet can be obtained by arranging the tape-like reinforcing fiber bundles drawn out from the bobbin. It also has a reinforcing fiber arrangement mechanism for orderly arranging reinforcing fiber bundles drawn from creeled bobbins, eliminating undesirable overlapping and folding of reinforcing fiber bundles in reinforcing fiber sheets, and gaps between reinforcing fiber bundles. Is preferred. As the reinforcing fiber arranging mechanism, a known roller or comb-type arranging device can be used. It is also useful to stack a plurality of pre-arranged reinforcing fiber sheets from the viewpoint of reducing the gap between the reinforcing fibers. The creel is preferably provided with a tension control mechanism when drawing out the reinforcing fibers. As the tension control mechanism, a known mechanism can be used, and a brake mechanism or the like can be used. The tension can also be controlled by adjusting the thread guide.

On the other hand, specific examples of the reinforcing fiber fabric include, in addition to woven fabric and knitted fabric, those in which reinforcing fibers are two-dimensionally arranged in a multiaxial manner, and those in which reinforcing fibers such as nonwoven fabric, mat, and paper are randomly oriented. . In this case, the reinforcing fibers can be formed into a sheet using a method such as binder application, entanglement, welding, or fusion. As the woven fabric, a non-crimp woven fabric, a bias structure, an entangled woven fabric, a multiaxial woven fabric, a multiple woven fabric, or the like can be used in addition to the plain woven fabric, twill fabric, and satin woven fabric. The woven fabric in which the bias structure and the UD base material are combined not only suppresses the deformation of the woven fabric due to the pulling in the process of applying (also referred to as application) a matrix resin and the impregnation process by the UD structure, but also performs the pseudo structure by the bias structure. It also has isotropy and is a preferred form. In addition, the multi-layer fabric has an advantage that the structure / characteristics of the fabric upper / lower surface and the inside of the fabric can be individually designed. In the case of a knitted fabric, warp knitting is preferred in consideration of the shape stability in the coating / impregnation step, but a blade which is a tubular knitted fabric can also be used.

Among these, when giving priority to the mechanical properties of FRP, it is preferable to use a UD substrate, and the UD substrate can be produced by a known method in which reinforcing fibers are arranged in a sheet shape in one direction. .

<Smoothing of reinforcing fiber sheet>
In the present invention, by increasing the surface smoothness of the reinforcing fiber sheet, it is possible to improve the uniformity of the applied amount of the matrix resin in the application section. For this reason, it is preferable to guide the reinforcing fiber sheet to the liquid pool after performing the smoothing treatment. The method of smoothing is not particularly limited, and examples thereof include a method of physically pressing with a facing roll or the like, and a method of moving a reinforcing fiber using an air flow. The physical pressing method is preferred because it is simple and does not easily disturb the arrangement of the reinforcing fibers. More specifically, calendering or the like can be used. The method using an air flow is preferable because it not only causes less abrasion but also has the effect of widening the reinforcing fiber sheet.

<Widening of reinforced fiber sheet>
In the present invention, it is also preferable to guide the reinforcing fiber sheet to the liquid pool after widening the reinforcing fiber sheet from the viewpoint of efficiently producing a thin prepreg. There is no particular limitation on the widening processing method, and examples thereof include a method of mechanically applying vibration and a method of expanding the reinforcing fiber bundle by an air flow. As a method of mechanically applying vibration, there is a method of bringing a reinforcing fiber sheet into contact with a vibrating roll as described in, for example, JP-A-2015-22799. As the vibration direction, when the traveling direction of the reinforcing fiber sheet is the X axis, it is preferable to apply vibrations in the Y axis direction (horizontal direction) and the Z axis direction (vertical direction). It is also preferable to use them in combination. It is preferable that a plurality of projections are provided on the surface of the vibrating roll, because the abrasion of the reinforcing fibers by the roll can be suppressed. As a method using an air flow, see, for example, SEN-I GAKKAISHI, vol. 64, P-262-267 (2008). The described method can be used.

<Preheating of reinforced fiber sheet>
Further, in the present invention, it is preferable that the reinforcing fiber sheet is heated and then guided to the liquid pool portion, because the temperature decrease of the matrix resin can be suppressed and the viscosity uniformity of the matrix resin can be improved. The reinforcing fiber sheet is preferably heated to a temperature close to the matrix resin temperature. Examples of heating means for this include air heating, infrared heating, far infrared heating, laser heating, contact heating, and heating medium heating (such as steam). Means can be used. Above all, infrared heating is preferable because the apparatus is simple and the reinforcing fiber sheet can be directly heated, so that it can be efficiently heated to a desired temperature even at a high running speed.

<Matrix resin>
The matrix resin used in the present invention can be used as a resin composition containing various resins and particles described below, a curing agent, and various additives. The prepreg obtained by the present invention is in a state in which the matrix resin is impregnated in the reinforcing fiber sheet, and can be laminated and molded as a sheet-shaped prepreg to obtain a member made of FRP. The degree of impregnation can be controlled by additional impregnation after the design of the application section and the application of the matrix resin. The matrix resin can be appropriately selected depending on the application, but it is common to use a thermoplastic resin or a thermosetting resin. The matrix resin may be a molten resin heated and melted or a matrix resin at room temperature. Further, a solution or a varnish formed using a solvent may be used.

As the matrix resin, a resin generally used for FRP such as a thermoplastic resin, a thermosetting resin, and a photocurable resin can be used. Further, these may be used as they are if they are liquids at room temperature, or may be used as solids or viscous liquids at room temperature to reduce the viscosity by heating, or may be used as a melt by melting, or a solvent. May be used as a solution or varnish.

The thermoplastic resin is selected from a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, a urethane bond, a urea bond, a thioether bond, a sulfone bond, an imidazole bond, and a carbonyl bond in the main chain. A polymer having a bond can be used. Specifically, polyacrylate, polyolefin, polyamide (PA), aramid, polyester, polycarbonate (PC), polyphenylene sulfide (PPS), polybenzimidazole (PBI), polyimide (PI), polyetherimide (PEI), polysulfone (PSU), polyether sulfone (PES), polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyaryl ether ketone (PAEK), polyamide imide (PAI), etc. it can. In fields requiring heat resistance such as aircraft applications, PPS, PES, PI, PEI, PSU, PEEK, PEKK, PEAK, and the like are suitable. On the other hand, for industrial applications and automotive applications, polyolefins such as polypropylene (PP), PA, polyester, PPS, and the like are preferable in order to increase molding efficiency. These may be polymers or oligomers or monomers for low viscosity and low temperature coating. Of course, these may be copolymerized depending on the purpose, or they may be mixed and used as a polymer blend or a polymer alloy.

Examples of the thermosetting resin include an epoxy resin, a maleimide resin, a polyimide resin, a resin having an acetylene terminal, a resin having a vinyl terminal, a resin having an allyl terminal, a resin having a nadic acid terminal, and a resin having a cyanate ester terminal. Can be These can be generally used in combination with a curing agent or a curing catalyst. In addition, these thermosetting resins can be appropriately used in combination.

エポキシ As a thermosetting resin suitable for the present invention, an epoxy resin is preferably used because of its excellent heat resistance, chemical resistance, and mechanical properties. In particular, an epoxy resin using an amine, a phenol, or a compound having a carbon-carbon double bond as a precursor is preferable. Specifically, as an epoxy resin using amines as a precursor, various isomers of tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, and triglycidylaminocresol, and phenols are used as precursors. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, a compound having a carbon-carbon double bond as a precursor Examples of the epoxy resin include, but are not limited to, alicyclic epoxy resins. Brominated epoxy resins obtained by brominating these epoxy resins are also used. An epoxy resin having an aromatic amine represented by tetraglycidyldiaminodiphenylmethane as a precursor has a good heat resistance and a good adhesion to a reinforcing fiber, and is most suitable for the present invention.

Thermosetting resin is preferably used in combination with a curing agent. For example, in the case of an epoxy resin, the curing agent may be a compound having an active group capable of reacting with an epoxy group. Preferably, a compound having an amino group, an acid anhydride group, or an azide group is suitable. Specifically, dicyandiamide, various isomers of diaminodiphenylsulfone, and aminobenzoic acid esters are suitable. More specifically, dicyandiamide is preferably used because of its excellent prepreg preservability. Further, various isomers of diaminodiphenyl sulfone are most suitable for the present invention because they give cured products having good heat resistance. As the aminobenzoic acid esters, trimethylene glycol di-p-aminobenzoate and neopentyl glycol di-p-aminobenzoate are preferably used. Although the heat resistance is lower than that of diaminodiphenyl sulfone, the tensile strength is lower. Because it is excellent, it is selected and used according to the application. It is also possible to use a curing catalyst if necessary. From the viewpoint of improving the pot life of the matrix resin, it is also possible to use a complexing agent capable of forming a complex with a curing agent or a curing catalyst.

In the present invention, it is also preferable to use a thermoplastic resin mixed with a thermosetting resin. A mixture of a thermosetting resin and a thermoplastic resin gives better results than using the thermosetting resin alone. This is because the thermosetting resin is generally capable of low pressure molding by an autoclave while having a brittle defect, whereas the thermoplastic resin is generally difficult to perform low pressure molding by an autoclave while having the advantage of being tough. This is because they exhibit a trade-off characteristic, that is, they can be used in combination to balance physical properties and moldability. When mixed and used, it is preferable to contain the thermosetting resin in an amount of more than 50% by mass from the viewpoint of the mechanical properties of the FRP obtained by curing the prepreg.

<Polymer particles>
Further, in the present invention, inorganic particles or organic particles can be contained in the matrix resin or the resin film. The type of the inorganic particles can be selected according to the purpose and is not particularly limited.For example, in order to impart conductivity, heat conductivity, thixotropy, and the like, carbon-based particles, boron nitride particles, titanium dioxide particles, silicon dioxide particles, and the like. Can be suitably used. The type of the organic particles may be selected according to the purpose, and is not particularly limited. Particularly, the use of polymer particles is preferable because the toughness, impact resistance, and vibration damping properties of the obtained FRP can be improved. At this time, it is preferable that the glass transition temperature (Tg) or the melting point (Tm) of the polymer particles be higher than the matrix resin temperature by 20 ° C. or more, because the shape of the polymer particles can be easily maintained in the matrix resin. The Tg of the polymer particles can be measured using a temperature-modulated DSC under the following conditions. As the temperature modulation DSC device, Q1000 manufactured by TA Instruments or the like is suitable, and it can be used after being calibrated with high-purity indium in a nitrogen atmosphere. The measurement conditions are as follows: the temperature rise rate is 2 ° C./min, and the temperature modulation condition is a cycle of 60 seconds and an amplitude of 1 ° C. The reversible component is separated from the total heat flow obtained in this way, and the temperature at the middle point of the step signal can be set to Tg.

Ｔ Further, Tm is measured by a normal DSC at a heating rate of 10 ° C / min, and the peak top temperature of a peak-like signal corresponding to melting can be defined as Tm.

Further, it is preferable that the polymer particles do not dissolve in the matrix resin. As such polymer particles, for example, appropriate ones can be used with reference to the description in WO2009 / 142231 pamphlet and the like. More specifically, polyamide or polyimide can be preferably used, and polyamide, which can greatly improve impact resistance due to excellent toughness, is most preferable. Polyamides such as polyamide 12, polyamide 11, polyamide 6, polyamide 66, polyamide 6/12 copolymer, and the epoxy compound described in Example 1 of JP-A-01-104624 are semi-IPN (polymer interpenetrating network structure). Polyamide (semi-IPN polyamide) or the like can be suitably used. The shape of the thermoplastic resin particles may be a spherical particle, a non-spherical particle, or a porous particle, but a spherical shape is particularly preferable in the production method of the present invention since the flow characteristics of the resin are not deteriorated. Further, a spherical shape is a preferable embodiment in that there is no starting point of stress concentration and high impact resistance is given.

Commercially available polyamide particles include SP-500, SP-10, TR-1, TR-2, 842P-48, 842P-80 (all manufactured by Toray Industries, Inc.) and "Orgasol (registered trademark)" 1002D. , 2001UD, 2001EXD, 2002D, 3202D, 3501D, 3502D (all manufactured by Arkema Co., Ltd.), "Grillamide (registered trademark)" TR90 (manufactured by Mazaverke Co., Ltd.), "TROGAMID (registered trademark)" CX7323, CX9701 , CX9704 (manufactured by Degussa Co., Ltd.) and the like can be used. These polyamide particles may be used alone or in combination of two or more.

ポリマー Further, in order to increase the toughness of the FRP interlayer resin layer, it is preferable to keep the polymer particles in the reinforcing fiber interlayer resin layer. Therefore, the number average particle size of the polymer particles is preferably in the range of 5 to 50 μm, more preferably in the range of 7 to 40 μm, and still more preferably in the range of 10 to 30 μm. When the number average particle diameter is 5 μm or more, the particles do not enter the bundle of the reinforcing fibers, and can remain in the reinforcing fiber interlayer resin layer of the obtained fiber-reinforced composite material. By setting the number average particle size to 50 μm or less, the thickness of the matrix resin layer on the prepreg surface can be optimized, and the fiber content in the obtained FRP can be optimized.

<Viscosity of matrix resin>
As the matrix resin used in the present invention, it is preferable to select an optimum viscosity from the viewpoint of processability and stability. Specifically, when the viscosity is in the range of 1 to 60 Pa · s, the dripping at the constricted portion exit can be suppressed, and the high-speed running property and the stable running property of the reinforcing fiber sheet can be improved, which is preferable. Here, the viscosity refers to a value measured at a matrix resin temperature in a liquid reservoir at a strain rate of 3.14 s ^-1 . As the measuring device, a viscoelasticity measuring device such as a parallel disk type or a cone type can be used. The viscosity of the matrix resin is more preferably 5 to 30 Pa · s.

<Process of applying matrix resin>
The process of applying the matrix resin with the UD substrate as an example of the reinforcing fiber sheet will be described with reference to FIG. 1. The method of applying the matrix resin 2 to the reinforcing fiber sheet 1 b in the coating apparatus 100 according to the example of FIG. After arranging the plurality of reinforcing fibers 1a unwound from the creel 11 in one direction (in the depth direction of the paper) by the arranging device 13, the reinforcing fiber sheet 1b is obtained. To apply the matrix resin 2 to both surfaces of the reinforcing fiber sheet 1b. Thereby, the primary prepreg 1c can be obtained. It goes without saying that the primary prepreg itself also corresponds to the prepreg according to the present invention. Here, the horizontal direction is shown as the X direction in FIG. Further, as described later, in the present invention, the reinforcing fiber sheet can be passed in the inclined direction, and traveling in the inclined direction and traveling in the horizontal direction can be combined. The tilt direction refers to a direction intermediate between the horizontal direction and the vertical direction. More specifically, the horizontal direction or the inclined direction can be in a range of −80 ° to + 80 ° with the horizontal plane being 0 °. If the running direction of the reinforcing fiber sheet in the constricted part in the application part is in the range of −30 ° to + 30 ° with the horizontal plane being 0 °, it becomes possible to incorporate the reinforcing fiber sheet into the existing prepreg manufacturing equipment, and from the viewpoint of versatility of equipment Is preferred. The running direction of the reinforcing fiber sheet in the constricted part in the application part is more preferably from −15 ° to + 15 ° with the horizontal plane as 0 °. Further, in FIG. 29 and the like described later, the reinforcing fiber sheet is introduced into the application section obliquely downward, and is also described as traveling in the vertical and oblique directions when traveling between the direction changing members in the application section. However, the running direction of the reinforcing fiber sheet is horizontal in a portion where the cross-sectional area is continuously reduced or in a narrow portion. When the reinforcing fiber sheet 1b is introduced horizontally to the application section 20 as shown in FIG. 1, the running path of the reinforcing fiber sheet 1b is linearized, and the reinforcing fiber sheet 1b is disturbed due to the thickness of the reinforcing fiber sheet 1b. Is less likely to occur. At this time, it is preferable to have a sealing mechanism so that the matrix resin 2 does not leak out at the introduction section of the reinforcing fiber sheet 1b into the application section 20.

The application section 20 includes an exit side member 29 facing the main body with a predetermined gap D therebetween, and the

wall side members

21a and 21b on the introduction side of the reinforcing fiber sheet 1b, and the exit side member 29 on the exit side. . Between the upper surface member 24 and the lower surface member 25, a liquid reservoir 22 and a slit-shaped constriction located on the outlet side of the liquid reservoir 22 and having a cross-sectional area smaller than the maximum cross-sectional area of the liquid reservoir 22. A part 23 is formed.

(4) In the application section 20, the reinforcing fiber sheet 1b introduced into the liquid pool section 22 travels in the horizontal direction while accompanying the matrix resin 2 around the reinforcing fiber sheet 1b. At that time, in the portion 22b of the liquid reservoir 22 where the cross-sectional area continuously decreases in the running direction of the reinforcing fiber sheet 1b, the accompanying matrix resin 2 is gradually compressed, and the outlet of the liquid reservoir 22 is , The pressure of the matrix resin 2 increases. When the pressure in the vicinity of the outlet of the liquid reservoir 22 increases, the accompanying liquid flow becomes more difficult to flow in the outlet direction, flows toward the upper member 24 and the lower member 25, and then flows toward the upper member 24 and the lower member 25. , And flows in the direction opposite to the running direction of the reinforcing fiber sheet 1b. As a result, in the liquid reservoir 22, a circulating flow T is formed along the plane of the reinforcing fiber sheet 1b and the wall surfaces of the upper member 24 and the lower member 25. As a result, even if the sheet-like reinforcing fibers 1 b bring the fluff into the liquid reservoir 22, the fluff moves along the circulation flow T, and approaches the vicinity of the outlet of the liquid reservoir 22 having a high hydraulic pressure and approaches the narrowed portion 23. Can not. When the reinforcing fiber sheet 1b is run at a high speed, the above-mentioned fluid pressure is further increased, so that the effect of preventing the fluff from approaching the vicinity of the outlet or the constriction 23 becomes higher. As a result, it becomes possible to apply the matrix resin 2 to the reinforcing fiber sheet 1b at a higher speed, and productivity is greatly improved.

{Circle around (4)} The increased liquid pressure has an effect that the matrix resin 2 is easily impregnated into the reinforcing fiber sheet 1b. This is based on the property (Darcy's law) that when a matrix material is impregnated into a porous body such as a reinforcing fiber bundle, the degree of impregnation increases with the pressure of the matrix resin. Also in this case, when the reinforcing fiber sheet 1b is run at a higher speed, the hydraulic pressure is further increased, so that the impregnation effect can be further enhanced. The matrix resin 2 is impregnated with the bubbles remaining inside the reinforcing fiber sheet 1b by gas / liquid displacement, and the bubbles have a continuous cross-sectional area with the portion 22a whose cross-sectional area does not decrease due to the circulating flow T and buoyancy. Are gathered near the boundary of the portion 22b. For this reason, it is preferable to install a degassing mechanism 26 for degassing air bubbles from the matrix resin 2 in the vicinity. More specifically, the installation position of the degassing mechanism is preferably within a range of 5 cm or less from the boundary position between the portion 22a where the cross-sectional area does not decrease and the portion 22b where the cross-sectional area continuously decreases. In Patent Document 3, impregnation is performed by a plurality of fixed guides, and it is considered that bubbles are generated in a wide range. However, a degassing mechanism is not necessarily installed in the vicinity thereof, and the removal of bubbles is not sufficient. There was a possibility.

Further, the reinforcing fiber sheet 1b is automatically centered at the center of the gap D by the increased hydraulic pressure, and the reinforcing fiber sheet 1b does not directly rub against the wall of the liquid reservoir 22 or the narrowed portion 23. It also has the effect of suppressing the generation of fluff. This is because, when the reinforcing fiber sheet 1b approaches one of the gaps D due to a disturbance or the like, the matrix resin 2 is pushed into the narrower gap on the approaching side and compressed, so that the hydraulic pressure increases on the approaching side. Then, the reinforcing fiber sheet 1b is pushed back to the center of the gap D.

The constriction 23 is designed to have a smaller cross-sectional area than the maximum cross-sectional area of the liquid reservoir 22. As can be understood from FIG. 1, the length of the quasi-plane of the reinforcing fiber sheet 1b in the perpendicular direction is small, that is, the cross-sectional area is small because the interval between the members is small. This is because the impregnation and the self-centering effect can be obtained by increasing the hydraulic pressure in the constricted portion 23 as described above. In addition, it is preferable that the cross-sectional shape of the entrance portion of the constricted portion 23 be made to match the cross-sectional shape of the surface of the liquid reservoir portion 22 in contact with the narrowed portion 23, from the viewpoint of the running property of the reinforcing fiber sheet 1b and the flow control of the matrix resin 2. Alternatively, the constriction 23 may be slightly larger if necessary.

Here, in the application section 20 in FIG. 1, the reinforcing fiber sheet 1b runs completely in the horizontal direction, but is not limited to this, and the above-described effects of collecting fluff and discharging bubbles can be obtained. 1b may travel in the inclined direction in the application section 20 within a range in which the vehicle can run stably continuously. Further, the application section 20 can be inclined.

Further, the total amount of the matrix resin 2 applied to the reinforcing fiber sheet 1b can be controlled by the gap D of the narrowed portion 23. For example, it is desired to increase the total amount of the matrix resin 2 applied to the reinforcing fiber sheet 1b (to increase the basis weight). In this case, the gap D may be adjusted to be wide.

FIG. 1 illustrates a case where one reinforcing fiber sheet is introduced into the application section from the horizontal direction. However, the introduction of the reinforcing fiber sheet into the application section is not limited to this, and a plurality of reinforcing fiber sheets may be used as necessary. And the introduction direction may be the inclined direction. This will be described with reference to FIGS.

には In FIG. 2, one reinforcing fiber sheet 1b runs obliquely downward from above and is introduced into the application section 20 through the opening 30. The running direction of the reinforcing fiber sheet 1 b is changed to a horizontal direction by the direction changing member 31, and the reinforcing fiber sheet 1 b is pulled out from the narrowed portion 23. It is preferable to introduce the reinforcing fiber sheet obliquely downward from the upper part of the application part because the matrix resin filled in the application part can be prevented from leaking by a simple method. Specifically, when the opening 30 is provided above the application section, a special sealing mechanism is not required, and the apparatus can be simplified. Of course, it is also possible to equip the opening with a sealing mechanism as required for various purposes such as filling the liquid pool with an inert gas. Further, it is preferable that at least the surface of the direction changing member 31 that is in contact with the reinforcing fiber sheet 1b is formed as a curved surface. In addition, from the viewpoint of preventing the wrapping of the reinforcing fiber sheet 1b, the direction changing member 31 is preferably fixed. For these reasons, the direction changing member 31 is preferably a fixed bar having a curved surface, and its cross-sectional shape can be exemplified by a circle, an ellipse, a saddle, and the like. Further, a curved surface and a flat surface may be mixed in a portion where the direction changing member 31 and the reinforcing fiber sheet 1b are in contact with each other, but when the ground start portion and the end portion of the reinforcing fiber sheet 1b are curved surfaces, generation of fluff can be suppressed. ,preferable. Furthermore, when the traveling speed is particularly increased, a rotatable roller can be used from the viewpoint of suppressing abrasion between the reinforcing fiber sheet 1b and the direction changing member 31.

Since the reinforcing fiber sheet 1b is pressed against the direction changing member 31, impregnation may be performed by replacing the gas in the reinforcing fiber sheet 1b with the matrix resin 2. In particular, as shown in FIG. 4, the impregnation can be promoted more efficiently by pressing the plurality of direction changing members 31 at an angle.

In addition, from the viewpoint of not obstructing the flow of the circulating flow T, the installation position of the direction changing member 31 is 1 cm or more from the boundary position between the portion 22a where the cross-sectional area does not decrease and the portion 22b where the cross-sectional area continuously decreases. It is preferable to use the portion 22a that does not decrease.

In FIG. 3, two reinforcing fiber sheets 1 b run obliquely downward from above and are introduced into the coating section 20 through the opening 30. The running direction of the two reinforcing fiber sheets 1b is changed by the direction changing member 31 to the horizontal direction, and after the two sheets are stacked, the two reinforcing fiber sheets 1b are pulled out from the narrowed portion 23. At this time, since the matrix resin 2 is contained and laminated between the two reinforcing fiber sheets 1b, the impregnation becomes easier to progress in the portion 22b and the constricted portion 23 where the cross-sectional area is continuously reduced, which is preferable.

Further, as described above, in the portion 22b where the cross-sectional area is continuously reduced, as the reinforcing fiber sheet 1b laminated with the matrix resin 2 interposed therebetween advances toward the outlet side, the liquid pressure becomes higher, so that the impregnation of the matrix resin 2 is performed. As the process proceeds, excess matrix resin 2 is squeezed out of the reinforcing fiber sheet 1b laminate, so that excessive swelling in the thickness direction can be suppressed. Thereby, it becomes possible to pull out the reinforced fiber sheet 1b laminate in the narrowed portion 23 without clogging in the thickness direction. This effect is particularly remarkable during high-speed running. To this end, it is important to gradually increase the hydraulic pressure at the portion 22b where the cross-sectional area continuously decreases. More specifically, the length H of the portion 22b where the cross-sectional area is continuously reduced is preferably 10 mm or more, from the viewpoint of suppressing excessive swelling in the thickness direction of the reinforcing fiber sheet 1b laminate, more preferably. Is 30 mm or more. If there is no portion 22b where the cross-sectional area is continuously reduced, the reinforcing fiber sheet 1b laminate containing the matrix resin 2 therein and having an excessive swelling in the thickness direction is rapidly introduced into the constricted portion 23. Therefore, the extra matrix resin 2 cannot be discharged, and if the gap D is thicker than the gap D, the matrix resin 2 is easily clogged. When the length H of the continuously decreasing portion 22b is less than 10 mm and the traveling speed of the reinforcing fiber sheet 1b is sufficiently low, the thickness of the reinforcing fiber sheet 1b laminate can be reduced. When the speed is increased, the effect becomes insufficient, and the clogging is likely to occur. As described above, when H is 30 mm or more, the traveling speed can be increased to 20 m / min or more.

In addition, the length C of the liquid pool portion (see FIG. 14) can be reduced within a range in which the reinforcing fiber sheet can travel, but specifically, the length C is set to 400 mm or less in order to reduce the volume of the liquid pool portion. Is preferred. More preferably, it is 200 mm or less.

には In FIG. 4, two reinforcing fiber sheets 1b run obliquely downward from above and are introduced into the coating section 20 through the opening 30. Then, the two reinforcing fiber sheets 1 b are impregnated while passing through the plurality of direction changing members 31, and are finally pulled out from the narrowed portion 23 after the two sheets are laminated. At this time, the shape and the number of the direction changing members 31 for promoting the impregnation can be variously selected according to the purpose. Further, the contact length between the direction changing member 31 and the reinforcing fiber sheet 1b and the angle (wrap angle) formed between both ends of the contact portion and the center of the direction changing member 31 can be selected according to the purpose.

、４ FIGS. 3 and 4 show an example in which the number of the reinforcing fiber sheets 1b is two, but it is needless to say that any number of the reinforcing fiber sheets 1b can be three or more.

FIG. 5 is a view of the application unit 20 viewed from the direction opposite to X in FIG. The coating portion 20 is provided with a side wall member 32 for preventing the matrix resin 2 from leaking from both ends in the arrangement direction of the reinforcing fiber sheet 1b, and a narrow portion is formed in the space surrounded by the outlet side member 29 and the side wall member 32. 23 outlets 28 are formed. Here, the outlet 28 has a slit shape, and the sectional aspect ratio (U / D in FIG. 5) may be set according to the shape of the reinforcing fiber sheet 1b to which the matrix resin 2 is to be applied.

FIG. 6 is a cross-sectional view illustrating the structure inside the coating unit when the coating unit 20 is viewed from the Z direction. In addition, the upper surface member 24 is omitted for easy viewing of the drawing.

FIG. 7 shows the flow of the matrix resin 2 in the gap 33 between the reinforcing fiber sheet 1b and the side wall member 32. If the gap 33 between the reinforcing fiber sheet 1b and the side wall member 32 is large, a vortex flows in the matrix resin 2 in the direction of R. The vortex flow R becomes outward flow (Ra) near the boundary between the portion 22b where the cross-sectional area is continuously reduced and the constricted portion 23 in the liquid reservoir 22, so that the reinforcing fiber sheet arranges the reinforcing fiber bundle. In the case of a reinforced fiber bundle (sheet-like reinforcing fiber bundle), the flow is in the direction of tearing (breaking of the sheet-like reinforcing fiber bundle). For this reason, the interval between the reinforcing fibers is widened, and when the prepreg is formed, the arrangement unevenness of the reinforcing fibers may occur. On the other hand, in the liquid reservoir 22, near the boundary between the portion 22a where the cross-sectional area does not decrease and the portion 22b where the cross-sectional area continuously decreases, an inward flow (Rb) occurs, so that the reinforcing fiber sheet 1b moves in the width direction. It may be compressed and its ends may break. In an apparatus typified by Patent Document 2 (Japanese Patent No. 3252278) for applying a matrix resin to both surfaces of an integral sheet-like base material (especially, a film), the reinforcing fiber sheet 1b and the side wall member 32 are formed. Even if a vortex flow occurs in the gap 33, there is little effect on the quality, and therefore, no attention was paid.

Therefore, in the present invention, it is important to control the width to reduce the gap 33 between the reinforcing fiber sheet 1b and the side wall member 32, and to suppress the generation of the vortex at the end. More specifically, the width L in the Y direction of the portion 22 b of the liquid reservoir 22 where the cross-sectional area is continuously reduced, that is, the interval L between the left and right side wall members 32 is the reinforcing fiber sheet measured at the outlet of the constriction 23. It is important to configure so as to satisfy the relationship of the width W of 1b and the following equation (1).
L ≦ W + 10 (mm) (1).

That is, an interval L between the left and right side wall members 32 (the width of the end of the liquid pool portion. However, if the surfaces forming the liquid pool portions of the left and right side wall members are not parallel, the width L is the width of the terminal of the liquid pool portion). The width W of the sheet-shaped reinforcing fiber bundle at the outlet of the constricted portion is set so as to satisfy the relationship of the above equation (1).

Thereby, generation of a vortex at the end is suppressed, cracking of the reinforcing fiber sheet 1b and breakage of the end can be suppressed, and the reinforcing fibers are uniformly arranged over the entire width (W) of the prepreg 1b. The prepreg 1d having high properties can be obtained. Furthermore, when this technology is applied to a prepreg, not only can the quality and quality of the prepreg be improved, but also the mechanical properties and quality of the FRP obtained using the prepreg can be improved. More preferably, when the relationship between L and W is L ≦ W + 2 (mm), cracks and end breaks in the reinforcing fiber sheet can be further suppressed.

下限 Further, it is preferable to adjust the lower limit of L to be not less than W-5 (mm) from the viewpoint of improving the uniformity of the dimension in the width direction of the prepreg 1d.

In addition, this width regulation is, from the viewpoint of suppressing the generation of the vortex R due to high hydraulic pressure at the outlet side of the portion 22b where the cross-sectional area continuously decreases, at least the G at the outlet side of the portion 22b where the cross-sectional area continuously decreases. (FIG. 6). Further, when the width regulation is more preferably performed in the entire area of the portion 22b where the cross-sectional area is continuously reduced, more preferably in the entire area of the liquid reservoir 22, the generation of the vortex R can be almost completely suppressed. As a result, it is possible to almost completely suppress cracks and end breaks in the reinforcing fiber sheet.

In addition, from the viewpoint of suppressing the vortex flow in the gap 33 between the reinforcing fiber sheet 1b and the side wall member 32, the width regulation may be limited to only the liquid pool portion 22, but if the narrow portion 23 is similarly performed, the primary prepreg 1c It is preferable from the viewpoint of suppressing the excessive matrix resin 2 from being applied to the side surface.

<Width regulation mechanism>
In the above, the case where the side wall member 32 plays the role of width regulation is shown. However, as shown in FIG. 8,

width regulation mechanisms

34a and 34b may be provided between the side wall members 32, and the width regulation may be performed by such a mechanism. This is preferable from the viewpoint that prepregs having various widths can be manufactured by one coating portion by allowing the width regulated by the width regulating mechanism to be freely changed. Here, the relationship between the width (W) of the reinforcing fiber sheet 1b at the outlet of the constricted portion 23 and the width (L2) regulated by the width regulating mechanism at the exit side end of the width regulating mechanism is L2 ≦ W + 10 (mm). It is more preferable that L2 ≦ W + 2 (mm). Further, the lower limit of L2 is preferably adjusted to be not less than W-5 (mm) from the viewpoint of improving the uniformity of the dimension in the width direction of the prepreg 1d.

Ｌ When the width regulating mechanism is used, L in the above equation (1) is regarded as L2.

形状 The shape and material of the width regulating mechanism are not particularly limited, but a plate-shaped bush is simple and preferable. Further, by having a width slightly smaller than the distance between the upper surface member 24 and the lower surface member 25 (refer to FIG. 8, the vertical length of the

width regulating mechanisms

34 a and 34 b in the figure viewed from the X direction). This is preferable because the horizontal flow of the matrix resin 2 can be prevented. On the other hand, it is possible to suppress the stagnation of the matrix resin 2 in the liquid pool by forming the shape along the internal shape of the liquid pool 22 from the middle portion of the width regulating mechanism to the outlet end, thereby preventing the matrix resin 2 from deteriorating. It is preferable because it can be suppressed. In this sense, it is preferable that the width regulating mechanism 34 is inserted to the constriction 23. FIG. 8 shows an example of a plate-shaped bush as the width regulating mechanism. An example in which the outlet side from the middle of the bush is inserted along the tapered shape of the portion 22b where the cross-sectional area is continuously reduced to the narrowed portion 23 is shown. Is shown. FIG. 8 shows an example in which L2 is constant from the vicinity of the boundary between the portion 22a where the cross-sectional area does not decrease and the portion 22b where the cross-sectional area continuously decreases to the exit. The width restricted by the control may be changed. The width regulating mechanism can be fixed to the application section 20 by an arbitrary method. However, in the case of a plate-shaped bush, fixing the plate at a plurality of portions in the running direction of the reinforcing fiber sheet 1b allows the plate shape to be formed by high hydraulic pressure. Variations in the regulation width due to deformation of the bush can be suppressed.

<Shape of liquid pool>
As described in detail above, in the present invention, the liquid pressure is increased in the running direction of the reinforcing fiber sheet by continuously decreasing the cross-sectional area in the running direction of the reinforcing fiber sheet 1b in the liquid reservoir 22. Is important. Here, the continuous decrease in the cross-sectional area in the running direction of the reinforcing fiber sheet is not particularly limited as long as the hydraulic pressure can be continuously increased in the running direction. In the cross-sectional view of the liquid reservoir, the liquid reservoir may have a curved shape such as a tapered shape (linear shape) or a trumpet shape. In addition, the cross-sectional area decreasing portion may be continuous over the entire length of the liquid pool portion, or may include a portion where the cross-sectional area does not decrease or a portion which expands conversely as long as the object and effects of the present invention can be obtained. You may go out. These will be described in detail below with reference to FIGS. 9 to 12. 9 to 12, the vicinity of the outlet is shown, and the vicinity of the introduction portion of the reinforcing fiber sheet 1b, the degassing mechanism, and the like are omitted.

FIG. 9 is a detailed cross-sectional view of the coating section 20 of FIG. When the portion 22b where the cross-sectional area of the liquid reservoir 22 is continuously reduced is tapered, the opening angle θ of the taper is preferably small, specifically, an acute angle (90 ° or less). θ is more preferably 30 ° or less. Thereby, the compression effect of the matrix resin 2 can be enhanced in the portion 22b (tapered portion) where the cross-sectional area of the liquid reservoir 22 is continuously reduced, and a high liquid pressure can be easily obtained.

FIG. 10 is a detailed cross-sectional view of the application section 20b of another embodiment different from FIG. It is the same as the application section 20 in FIG. 9 except that the shape of the portion 22b where the cross-sectional area is continuously reduced is a two-step tapered shape. As described above, the portion 22b where the cross-sectional area of the liquid reservoir 22 is continuously reduced may be configured by a multi-stage taper portion having two or more stages. At this time, it is preferable to make the opening angle θ of the tapered portion closest to the constricted portion 23 an acute angle from the viewpoint of enhancing the compression effect. Also in this case, it is preferable that the length H of the portion 22b where the cross-sectional area of the liquid reservoir 22 is continuously reduced is 10 mm or more. More preferably, the length H of the portion 22b where the cross-sectional area is continuously reduced is 30 mm or more. As shown in FIG. 10, the portion 22 b where the cross-sectional area of the liquid reservoir 22 is continuously reduced is formed into a multi-stage tapered portion, so that the volume of the matrix resin 2 that can be stored in the liquid reservoir 22 is maintained while the constriction portion 23 is maintained. Can be further reduced. As a result, the liquid pressure generated on the outlet side of the liquid reservoir 22 is further increased, and the effect of eliminating fluff and the effect of impregnating the matrix resin 2 can be further enhanced.

FIG. 11 is a detailed cross-sectional view of the application unit 20c according to another embodiment different from FIG. It is the same as the application section 20 in FIG. 9 except that the shape of the portion 22b where the cross-sectional area is continuously reduced is stepped. As described above, if there is a portion 22b having a continuously decreasing cross-sectional area at the most outlet side of the liquid reservoir 22, the effect of increasing the liquid pressure, which is the object of the present invention, can be obtained. The portion may include a portion 22c whose cross-sectional area decreases intermittently.

FIG. 12 is a detailed cross-sectional view of the application unit 20d according to another embodiment different from FIG. It is the same as the application section 20 in FIG. 9 except that the shape of the portion 22b where the cross-sectional area is continuously reduced is a trumpet shape (curved shape). In the application section 20 of FIG. 9, the portion 22b where the cross-sectional area of the liquid reservoir 22 continuously decreases is tapered (linear), but is not limited to this. For example, a trumpet shape (curved shape) as shown in FIG. May be. However, it is preferable that the portion 22b having a continuously reduced cross-sectional area and the constricted portion 23 be connected smoothly. This is because if there is a step at this boundary, the reinforcing fiber sheet 1b is caught on the step, and there is a concern that fluff is generated at this portion. When the portion 22b in which the cross-sectional area of the liquid reservoir 22 is continuously reduced has a trumpet shape, the virtual tangent at the most outlet side of the portion 22b in which the cross-sectional area of the liquid reservoir 22 is continuously reduced. It is preferable to make the opening angle θ of the first angle acute.

In the above description, an example in which the cross-sectional area is smoothly reduced has been described. However, in the present invention, the cross-sectional area of the liquid reservoir does not necessarily have to be smoothly reduced unless the object of the present invention is impaired.

FIG. 13 is a detailed cross-sectional view of the application section 40 of another embodiment different from the present invention. Unlike the embodiment of the present invention, the liquid pool 41 in FIG. 13 does not include a portion where the cross-sectional area continuously decreases in the running direction (X direction) of the reinforcing fiber sheet, and is cut off at the boundary 42 with the narrowed portion 23. The area is discontinuous and sharply reduced. Therefore, the reinforcing fiber sheet 1b is easily clogged.

When the matrix resin stored in the liquid reservoir is easily denatured by heat or the like, it is preferable to reduce the volume of the liquid reservoir as much as possible from the viewpoint of the quality stability of the obtained prepreg and the process stability of coating. preferable. On the other hand, if the volume of the liquid reservoir is excessively reduced, it may be assumed that the supply of the matrix resin to the liquid reservoir is likely to be insufficient with respect to the applied amount. In such a case, there is a possibility that the circulating flow in the liquid pool portion becomes uneven, and the running property of the reinforcing fiber sheet becomes poor. In addition, when the entire coating section is heated, a gap is generated between the upper surface member 24 and the liquid surface of the liquid pool section 22, causing non-uniformity in the temperature of the matrix resin 2, and the quality stability of the obtained prepreg. In addition, there is a possibility that the process stability of the coating becomes poor. For this reason, it is preferable to reduce the volume of the liquid reservoir and balance the supply amount and the application amount of the matrix resin to the liquid reservoir. From this point of view, it is preferable to provide the storage portion 43 of the matrix resin 2 near the opening 30 while reducing the volume of the liquid pool portion, for example, as in the application portion 20e shown in FIG. By making the shape of the storage section 43 vertically long, the detection of the liquid level 44 of the matrix resin 2 becomes easy, and the management of the storage amount of the matrix resin 2 by managing the liquid level becomes easy. By feeding back the position of the liquid surface to the matrix resin supply system, it is possible to balance the supply amount and the supply amount of the matrix resin to the liquid reservoir. The storage portion 43 for this purpose can be formed by, for example, the wall member 21 and the upper surface member 24, but is not limited thereto. From the viewpoint of minimizing the storage amount of the matrix resin, the distance B defined by the lower surface of the upper surface member 24 and the upper surface of the storage portion 43 in FIG. 14 is preferably 100 mm or less, and the traveling path of the reinforcing fiber sheet 1b. In consideration of the degree of freedom of design, it is preferably 50 mm or less.

It is also preferable to add a mechanism for removing the fluff of the reinforcing fiber sheet in the application section. Further, it is preferable to add a mechanism for discharging the excess matrix resin.

<Resin film and release sheet application process>
In the present invention, it is possible to further apply a resin film or a release sheet to the primary prepreg 1c drawn out of the matrix resin applying step. The example of FIG. 1 shows a case where a resin film 4 is provided on one surface and a release sheet 3 is provided on the other surface. In this example, the resin film 4 is supplied from the supply device 16b, the release sheet 3 is supplied from the supply device 16a, and the release film 3 can be stacked on the transport roll 15 on the primary prepreg 1c. Although the example of FIG. 1 shows an example in which one resin film 4 and one release sheet 3 are laminated, depending on the purpose, only the resin film 4 or only the release sheet 3 is laminated. Alternatively, the resin film may be laminated on both sides, or the release sheet may be laminated on both sides. Further, a mode in which the resin film and the release sheet are laminated may be employed. The type of resin constituting the resin film can be appropriately selected according to the purpose, and may be a mixture of a plurality of types of resins. When two resin films are used, they may be the same resin film or different types of resin films. When two release sheets are used, they may be of the same type or different types.

On the other hand, as the release sheet, a sheet formed of a polymer having a release action or a sheet in which a release layer is provided on a substrate, for example, a sheet in which a release layer is laminated on the resin film described above is used. It can also be supplied. Of course, the above description is not limited to the embodiment of FIG. 1, and the same can be applied to the embodiments of other drawings.

において In the present invention, the resin used for the resin film is not particularly limited, and can be appropriately selected depending on the purpose. The resin used as the resin film may be a single resin, a blend of different polymers, or a resin composition that is a blend of various components. The resin film used here can contain the particles. When a matrix resin containing particles is used in the application step, the viscosity tends to increase, and the uniformity of application may be deteriorated during high-speed running of the reinforcing fiber sheet. For this reason, it is preferable to apply the particles in the resin film applying step because the high-speed running stability of the reinforcing fiber sheet in the applying step is improved. At this time, the resin film containing particles may be a resin film made of a matrix resin. By doing so, the matrix resin can be applied while the particles are applied separately from the coating step, so that it is efficient. At this time, the matrix resin of the matrix resin containing particles may be the same as or different from the matrix resin component used in the coating step. The components of the matrix resin used in the coating step and the matrix resin to be formed into a resin film can be adjusted in consideration of the high-speed running stability in the coating step and the pot life in storage in the coating section.

Alternatively, a certain resin component can be taken out of the matrix resin and formed into a resin film. For example, in FRP, a thermoplastic resin can be blended with a matrix resin mainly composed of a thermosetting resin to improve the toughness of the resin. However, this thermoplastic resin may increase the viscosity of the matrix resin. In such a case, application stability can be improved by applying the thermoplastic resin as a resin film to the primary prepreg without using it as a component of the matrix resin applied in the application step. PES, PEI, PI, and the like are often used as such a thermoplastic resin. In addition, such a thermoplastic resin film may be a self-supporting film that does not require a support in some cases, and is useful from the viewpoint that the support can be omitted.

The method for obtaining the resin film is not particularly limited, and a known method can be used.For example, using a known coater such as a roll coater, a comma coater, a knife coater, a die coater, and a spray coater, film formation is performed. You can do it. Further, if necessary, a resin can be applied on a support such as a release sheet to form a film.

<Travel mechanism>
As a traveling mechanism for transporting the reinforcing fiber sheet or the prepreg of the present invention, a known roller or the like can be suitably used. In the present invention, since the reinforcing fiber sheet is conveyed in the horizontal direction or the inclined direction, it is preferable to arrange rollers before and after the application section.

In the present invention, it is preferable that the running path of the reinforcing fiber sheet is as straight as possible in order to suppress the arrangement disorder and the fluffing of the reinforcing fiber. In addition, the prepreg is often a sheet-like integrated body that is a laminate with a release sheet, but in the conveying step of the prepreg, if there is a bent portion, wrinkles may occur due to a difference in circumference between the inner layer and the outer layer. Therefore, it is preferable that the traveling path of the sheet-shaped integrated object is as straight as possible. From this viewpoint, it is preferable to use a nip roll in the traveling path of the sheet-like integrated object.

Whether the S-shaped roll or the nip roll is used can be appropriately selected according to the manufacturing conditions and the characteristics of the product.

<High tension take-up device>
In the present invention, it is preferable to arrange a high tension take-up device for drawing out the prepreg from the application section downstream of the application section. This is because high frictional force and shear stress are generated between the reinforcing fiber sheet and the matrix resin in the application section, and it is preferable to generate a high take-up tension downstream of the process in order to overcome the drawback and draw out the prepreg. It is. As the high tension take-up device, a nip roll, an S-shaped roll, a belt press, or the like can be used. In any case, by increasing the frictional force between the device and the prepreg, slip can be prevented and stable running can be achieved. For this purpose, it is preferable to arrange a material having a high coefficient of friction on the surface of the apparatus or to increase the pressure applied to the prepreg. From the viewpoint of preventing slippage, the belt press is reliable. On the other hand, the S-shaped roll is preferable because the frictional force can be easily controlled by the roll diameter and the contact length.

<Release sheet feeding device, winder>
In the production of a prepreg or FRP using the present invention, a release sheet feeding device or a winder can be used as appropriate, and as such a device, a known device can be used. It is preferable to provide a mechanism capable of feeding back the winding tension or feeding back the winding speed from the viewpoint of stable running of the sheet.

<Addition impregnation>
In order to adjust the degree of impregnation to a desired degree, it is also possible to combine a means for further increasing the degree of impregnation using an impregnating apparatus separately after coating with the present invention. Here, in order to distinguish it from the impregnation in the application section, additional impregnation after application is referred to as additional impregnation, and an apparatus therefor is referred to as an additional impregnation apparatus. The device used as the additional impregnation device is not particularly limited, and can be appropriately selected from known devices according to the purpose. For example, as described in JP-A-2011-132389 and WO2015 / 060299, a laminate of a sheet-like carbon fiber bundle and a resin is preheated by a hot plate to sufficiently soften the resin on the sheet-like carbon fiber bundle. The impregnation can also be advanced by using a device that presses with a heated nip roll. The temperature of the hot plate for preheating, the surface temperature of the nip roll, the linear pressure of the nip roll, and the diameter and number of the nip rolls can be appropriately selected so as to obtain a desired impregnation degree. It is also possible to use an "S-wrap roll" in which a prepreg sheet runs in an S-shape as described in WO 2010/150022 pamphlet. In the present invention, “S-wrap roll” is simply referred to as “S-shaped roll”. WO 2010/150022 Pamphlet FIG. 1 shows an example in which the prepreg sheet runs in an S-shape, but if impregnation is possible, the contact length between the sheet and the roll, such as a U-shape, V-shape or Λ-shape, is described. May be adjusted. When the impregnation pressure is increased to increase the degree of impregnation, it is also possible to add an opposing contact roll. Further, as shown in FIG. 4 of the pamphlet of WO 2015/076981, it is possible to improve the impregnation efficiency by arranging the conveyor belt opposite to the “S-wrap roll” and to increase the production speed of the prepreg. In addition, as described in WO 2017/068159 pamphlet and JP-A-2016-20397, etc., it is possible to improve the impregnation efficiency by applying ultrasonic waves to the prepreg before the impregnation and rapidly raising the temperature of the prepreg. is there. Further, as described in JP-A-2017-154330, it is also possible to use an impregnation device that vibrates a plurality of "ironing blades" with an ultrasonic generator. It is also possible to fold and impregnate the prepreg as described in JP-A-2013-22868.

<Simple additional impregnation>
In the above, an example in which the conventional additional impregnation apparatus is applied has been described. However, the temperature of the primary prepreg may still be high immediately after the application section, and in such a case, it takes a long time after leaving the application section. If an additional impregnation operation is added at a stage where the primary prepreg is not heated, a heating device such as a hot plate for reheating the primary prepreg can be omitted or simplified, and the impregnation device can be greatly simplified and downsized. Such an impregnation device located immediately after the application section is referred to as a simple additional impregnation device. As a simple additional impregnating device, a heated nip roll or a heated S-shaped roll can be used, but the roll diameter, the set pressure, and the contact length between the primary prepreg and the roll can be reduced as compared with a normal impregnating device. This is preferable because not only the size can be reduced but also the power consumption and the like can be reduced.

Also, it is preferable to apply a release sheet to the primary prepreg before the primary prepreg enters the simple additional impregnating apparatus, because the running property of the primary prepreg is improved.

FIG. 17 shows an example of a prepreg manufacturing process equipped with a simple additional impregnation device. A simple additional impregnation device 453 is provided immediately after the application section 430. Here, the simple additional impregnation device 453 shows an example of a nip roll, but the nip roller preferably has a heating mechanism. The number of nip rolls can be appropriately selected depending on the purpose, but from the viewpoint of simplification of the process, three or less nip rolls are preferable (FIG. 17 shows an example of two nip rolls). Further, it is preferable that the nip roller is provided with a driving device from the viewpoint that tension control of prepreg conveyance is easy. The nip pressure can be appropriately adjusted according to the desired degree of impregnation.

(4) It is preferable that the nip roll surface is subjected to an appropriate release treatment so that the primary prepreg does not stick, or a release sheet is inserted between the primary prepreg and the nip roll. When the release sheet is inserted between the primary prepreg and the nip roll, the release sheet can be inserted from the application section 430 side and the release sheet can be separated from the primary prepreg by the roll on the high tension take-off device 444 side. The separated release sheet may be wound up as it is, or may be run again on the circuit so as to be inserted again from the application section 430 side.

追 In addition to the nip roll, the above-mentioned “S-wrap roll”, a fixed bar, or the like can be used as the additional impregnation device.

<Prepreg>
The prepreg referred to in the present invention is a reinforced fiber sheet provided with a matrix resin, and is a two-dimensional sheet-like intermediate substrate for producing FRP. In the present invention, a so-called drawn material (pull extrusion) is also included in the prepreg without departing from this meaning. Further, as described later, the width of the prepreg is not particularly limited, and the prepreg may be manufactured in a narrow tape shape or a wide width up to about 2 m. The thickness of the prepreg is not particularly limited, but is generally about 0.05 mm to 1 mm.

において In the prepreg obtained by the production method of the present invention, the impregnation ratio of the matrix resin is desirably 10% or more. The state of the impregnation of the matrix resin can be confirmed by tearing the collected prepreg and visually observing the inside, and can be more quantitatively evaluated by, for example, a peeling method. The impregnation rate of the matrix resin by the peeling method can be measured as follows. That is, the collected prepreg is sandwiched between adhesive tapes, and the prepreg is peeled off to separate the reinforcing fibers to which the matrix resin has adhered from the reinforcing fibers to which the matrix resin has not adhered. Then, the ratio of the mass of the reinforcing fibers to which the matrix resin has adhered to the mass of the entire reinforcing fiber sheet put in can be taken as the impregnation rate of the matrix resin by the peeling method. In the case of a prepreg having a high degree of impregnation, the degree of impregnation can also be evaluated based on the water absorption due to the capillary action of the prepreg. Specifically, in accordance with the method described in JP-T-2016-510077, the prepreg can be cut into 10 cm × 10 cm, one side of which is 5 mm, and can be calculated from the change in mass when immersed in water for 5 minutes. .

<Prepreg width>
The width of the prepreg is not particularly limited, and may be a wide width of about several tens cm to 2 m, or a tape having a width of several mm to several tens mm. The width can be selected according to the application. In recent years, devices called ATL (Automated Tape Laying) or AFP (Automated Fiber Placement) for automatically laminating narrow-width prepregs and prepreg tapes have been widely used in order to streamline the prepreg lamination process. Therefore, it is also preferable that the width is adjusted to this. ATL often uses narrow prepregs having a width of about 7.5 cm, about 15 cm, or about 30 cm. AFP often uses prepreg tapes having a width of about 3 mm to about 25 mm.

There is no particular limitation on the method of obtaining a prepreg having a desired width, and a method of slitting a wide prepreg having a width of about 1 to 2 m into a narrow width can be used. Further, in order to simplify or omit the slitting step, the width of the coating portion used in the present invention can be adjusted so as to have a desired width from the beginning. For example, when manufacturing a narrow prepreg having a width of 30 cm for ATL, the width of the application section outlet may be adjusted accordingly. In addition, in order to manufacture this efficiently, it is preferable to manufacture the product with a product width of 30 cm. When a plurality of such manufacturing devices are arranged in parallel, the same traveling device / transport device, various rolls, and a winder are used. The prepreg of the line can be manufactured.

FIG. 18 shows an example in which five application units are connected in parallel in one example. At this time, the five reinforced fiber sheets 416 may pass through five independent application parts 430 to obtain five primary prepregs 471, or the application parts 430 may be integrated in a parallel direction. It may be. In this case, the coating unit 430 may be provided with five independent width control mechanisms and five coating unit outlet widths.

In the case of a prepreg tape, a reinforcing fiber sheet in the form of a tape-shaped reinforcing fiber bundle having about 1 to 4 yarns is formed and passed through a coating section whose width has been adjusted so as to obtain a desired tape width. You can also get it. In the case of a prepreg tape, in particular, the accuracy of the tape width is often required from the viewpoint of controlling the lateral overlap between the tapes. For this reason, it is preferable to more strictly control the outlet width of the application section. In this case, it is preferable that the above L, L2, and W satisfy the relationship of L ≦ W + 1 mm and / or L2 ≦ W + 1 mm. .

<Slit>
The method of slitting the prepreg is not particularly limited, and a known slit device can be used. After winding the prepreg once, it may be installed in the slit device again to perform slitting, or for efficiency, a slit step may be arranged continuously from the prepreg production step without winding the prepreg once. Also, in the slitting step, a wide prepreg of 1 m or more may be directly slit to a desired width, or once cut and divided into narrow prepregs of about 30 cm, and then slit again to a desired width. good.

In addition, when the above-mentioned narrow prepreg and prepreg tape are arranged in a plurality of coating portions in parallel, a release sheet may be supplied independently, or one wide release sheet may be supplied. A plurality of prepregs may be stacked. The end in the width direction of the prepreg thus obtained can be cut off and supplied to an ATL or AFP device. In this case, since most of the cut edge is a release sheet, the matrix resin component (resin component in the case of FRP) adhering to the slit cutter blade can be reduced, and the cleaning cycle of the slit cutter blade is extended. There is also an advantage that you can do it.

<Modifications and Variations of the Present Invention>
In the present invention, by using a plurality of coating sections, it is possible to further improve the efficiency of the manufacturing process and to enhance the functions.

For example, a plurality of application sections can be arranged such that a plurality of prepregs are stacked. FIG. 19 shows an example of an embodiment in which prepregs are stacked using two application sections. The two primary prepregs 471 pulled out from the first coating unit 431 and the second coating unit 432 pass through the direction change roll 445 and are stacked by the stacking roll 447 downstream thereof. At this time, it is preferable to position the release sheet between the primary prepreg 471 and the direction change roll, because it is possible to suppress the prepreg from sticking to the roll and to stabilize traveling. The direction change roll can be replaced with a direction change guide or the like subjected to a release treatment.By using such a laminated prepreg, the efficiency of the prepreg laminating step can be improved, This is effective, for example, when manufacturing a thick FRP. Further, it is expected that the toughness and impact resistance of the FRP will be improved by laminating thin prepregs in multiple layers, and by applying the present production method, thin multilayer prepregs can be efficiently obtained. Further, by easily laminating different types of prepregs, a hetero-bonded prepreg having added functionality can be easily obtained. In this case, it is possible to change the type and fineness of the reinforcing fiber, the number of filaments, mechanical properties, fiber surface characteristics, and the like. It is also possible to use a different matrix resin (resin in the case of prepreg). For example, a prepreg having a different thickness or a heterojunction prepreg obtained by laminating prepregs having different mechanical properties can be used. In addition, a resin having excellent mechanical properties is provided in the first application section, and a resin having excellent tack properties is provided in the second application section. Obtainable. Conversely, it is also possible to arrange a resin having no tackiness on the surface. Further, a resin without particles can be applied in the first application section, and a resin containing particles can be applied in the second application section.

As another embodiment, as illustrated in FIG. 18 and described above, a plurality of application sections are arranged in parallel to the running direction of the reinforcing fiber sheet, that is, a plurality of application sections are arranged in parallel in the width direction of the reinforcing fiber sheet. Can be. This makes it possible to efficiently manufacture narrow or tape-shaped prepregs. Further, by changing the reinforcing fibers and the matrix resin for each application section, it is possible to obtain prepregs having different properties in the width direction.

As another mode, a plurality of application portions can be arranged in series in the running direction of the reinforcing fiber sheet. With such a serial arrangement, the type of matrix resin can be changed in the thickness direction of the primary prepreg. Even with the same type of matrix resin, running stability and high-speed running performance can be improved by changing the application conditions depending on the application section. For example, a resin having excellent mechanical properties is applied in the first application section, a resin having excellent tack properties is applied in the second application section, and a prepreg that can achieve both mechanical properties and tackiness by laminating them is easily provided. Obtainable. Conversely, it is also possible to arrange a resin having no tackiness on the surface. Alternatively, a resin without particles can be applied in the first application section, and a resin containing particles can be applied in the second application section.

いくつか As described above, several modes for disposing a plurality of application sections have been described. However, the number of application sections is not particularly limited, and various applications can be applied according to purposes. Of course, these arrangements can be combined. Furthermore, various sizes and shapes of the application section and application conditions (temperature, etc.) can be mixed and used.

As described above, the manufacturing method of the present invention is not only capable of improving the efficiency and stabilization of the manufacturing, but also is capable of improving the performance and functioning of the product, and is a manufacturing method excellent in expandability.

<Matrix resin supply mechanism>
In the present invention, the matrix resin is stored in the coating section, but it is preferable to appropriately supply the matrix resin because the coating proceeds. The mechanism for supplying the matrix resin to the application section is not particularly limited, and a known device can be used. It is preferable that the matrix resin be continuously supplied to the application section because the running of the reinforcing fiber sheet can be stabilized without disturbing the liquid level above the application section. For example, the self-weight can be supplied as a driving force from a tank storing the matrix resin, or can be supplied continuously using a pump or the like. As the pump, a gear pump, a tube pump, a pressure pump, or the like can be used as appropriate according to the properties of the matrix resin. When the matrix resin is solid at room temperature, it is preferable to provide a melter above the reservoir. Further, a continuous extruder or the like can be used. Further, it is preferable to provide a mechanism capable of continuously supplying the matrix resin in accordance with the applied amount so that the liquid level above the application portion of the matrix resin is as constant as possible. For this purpose, for example, as described above, a mechanism that monitors the liquid level, the weight of the application section, and the like and feeds it back to the supply device can be considered.

<Online monitoring>
Further, it is preferable to provide a mechanism capable of online monitoring of the application amount for monitoring the application amount. The online monitoring method is not particularly limited, and a known method can be used. For example, as a device for measuring the thickness, for example, a beta-ray meter or the like can be used. In this case, it is possible to estimate the coating amount by measuring the thickness of the reinforcing fiber sheet and the thickness of the prepreg and analyzing the difference. The application amount monitored online is immediately fed back to the application section, and can be used for adjusting the temperature of the application section and the gap D (see FIG. 1) of the constricted section 23. Application amount monitoring can of course be used as defect monitoring. As the thickness measurement position, for example, in FIG. 15, the thickness of the reinforcing fiber sheet 416 is measured before being introduced into the application section 430, and the thickness of the prepreg is measured between the application section 430 and the high tension take-up device 444. can do. It is also preferable to perform online defect monitoring using infrared rays, near infrared rays, a camera (image analysis), or the like.

The coating apparatus of the present invention has a traveling mechanism for causing a reinforcing fiber sheet in which reinforcing fibers are arranged in one direction to travel vertically downward, and an application mechanism, and the application mechanism can store a matrix resin therein. And further comprising a liquid reservoir and a constricted portion which are communicated with each other, wherein the liquid reservoir has a portion whose cross-sectional area continuously decreases along the running direction of the reinforcing fiber sheet, and wherein the constricted portion is , Having a slit-shaped cross section and having a smaller cross-sectional area than the upper surface of the liquid reservoir.

Hereinafter, the present invention will be described in more detail with specific examples of the production of a prepreg using the coating apparatus. Note that the following is an example, and the present invention is not construed as being limited to the embodiments described below.

FIG. 15 is a schematic view of an example of a prepreg manufacturing process / apparatus using the present invention. The plurality of reinforcing fiber bobbins 412 are hung on a creel 411, and are pulled out via a direction changing guide 413. At this time, the reinforcing fibers 414 can be pulled out at a constant tension by a brake mechanism provided to the creel. The plurality of pulled out reinforcing fibers 414 are orderly arranged by the reinforcing fiber arrangement device 415, and the reinforcing fiber sheet 416 is formed. In FIG. 15, only three yarns are drawn for the reinforcing fibers, but in practice, one to several hundred yarns can be used, and the prepreg width and the fiber weight can be adjusted to a desired value. . After that, it is guided to the reinforcing fiber sheet preheating device 420 and the coating unit 430 via the conveying roller 419 via the widening device 417 and the smoothing device 418. The reinforcing fiber sheet preheating device 420 can be used to match the temperature of the matrix resin in the application section with the temperature of the reinforcing fiber sheet as much as possible, but can be omitted. In FIG. 15, the reinforcing fiber sheet 416 is conveyed linearly from the reinforcing fiber arrangement device 415 to the conveying roll 419 between the devices. Note that the widening device 417 and the smoothing device 418 can be appropriately skipped or the devices can be omitted depending on the purpose. The arrangement order of the reinforcing fiber arrangement device 415, the widening device 417, and the smoothing device 418 can be appropriately changed according to the purpose. The reinforcing fiber sheet 416 travels obliquely downward from the transport roll 419, and reaches the high tension take-up device 444 via the application unit 430. The application section 430 can adopt any application section shape as long as the object of the present invention is achieved. For example, the shapes as shown in FIGS. 9 to 12, FIG. 14, FIG. 27, FIG. 29, and FIG. Further, if necessary, a width regulating mechanism can be provided as shown in FIG. In FIG. 15, the release sheet or the resin film 446 unwound from the

supply devices

442 and 443 can be laminated on the primary prepreg 471 on the high tension take-up device 444. Here, the resin film and the release sheet may be used alone or as a laminate of the resin film and the release sheet. At this time, it is preferable to make the resin surface adhere to the prepreg surface. A release paper, a release film, or the like can be used as the release sheet. In FIG. 15, a nip roll is drawn as the high tension take-up device 444. Thereafter, the sheet-like integrated material passes through an additional impregnating device 450 provided with a hot plate 451 and a heating nip roll 452, is cooled by a cooling device 461, is taken off by a take-off device 462, and peels off the upper release sheet 446. Then, a sheet-like integrated body 472 composed of a prepreg / release sheet as a product can be obtained by winding with a winder 464. Since the sheet-like integrated object is conveyed in a basic straight line from the high tension take-up device 444 to the winder 464, the occurrence of wrinkles can be suppressed. In FIG. 15, illustrations of the matrix resin supply device and the online monitoring device are omitted.

FIG. 16 is a schematic view of another example of a prepreg manufacturing process / apparatus using the present invention. FIG. 16 depicts an example in which two S-2 rolls 455 of the "S-wrap roll" type are used as the additional impregnation device (two rolls in total), but the number of rolls depends on the purpose. Can be increased or decreased. Further, in FIG. 16, a contact roll 456 for enhancing the impregnation effect is also drawn, but it is of course possible to omit it depending on the purpose.

FIG. 17 is a schematic view of another example of a prepreg manufacturing process / apparatus using the present invention. Here, an example using a simple additional impregnation device is shown. In FIG. 17, since the simple additional impregnation device 453 is installed immediately after the coating section 430, the prepreg 471 is guided to the simple additional impregnation device 453 in a high temperature state, so that the impregnation device can be simplified and downsized. In FIG. 17, the heating nip roll 454 is drawn as an example, but a small heating S-shaped roll may be used depending on the purpose. The use of the simple additional impregnation apparatus is also advantageous in that the entire prepreg manufacturing apparatus can be made very compact. In particular, when the resin film 446 is a particle-containing resin film, it is preferable to increase the degree of impregnation of the primary prepreg, because the particles in the resin film can be arranged on the prepreg surface layer in the next step.

Hereinafter, an example of the embodiment of the present invention, in which the effect of a portion of the liquid pool portion where the cross-sectional area is intermittently reduced, is verified by simulation will be described.

In performing the simulation, STAR-CCM + manufactured by SIMENS was used as software, and the Navier-Stokes equation was solved to numerically analyze the liquid flow and the liquid pressure at the portion where the cross-sectional area decreases intermittently. More specifically, a portion where the cross-sectional area decreases intermittently is modeled as a fluid portion, and a two-dimensional flow, that is, a fluid (matrix resin) flows only in the XZ plane and does not flow in the Y direction. It was assumed that. At this time, the viscosity of the fluid was 10 Pa · s, the density was 1000 kg / m ³ , and the running speed of the reinforcing fiber sheet was 20 m / min. FIGS. 20 and 21 show the analysis results when θ = 30 ° and H = 50 mm. In addition, since this analysis assumed plane symmetry with respect to the reinforcing fiber sheet, only the upper half is shown in the figure.

よう As shown in FIG. 20, in the portion of the liquid reservoir where the cross-sectional area decreases intermittently, the hydraulic pressure increases toward the outlet side, and the maximum hydraulic pressure is also as high as 0.782 MPa. In addition, as shown in FIG. 21, it can be seen that the accompanying flow of the reinforcing fiber sheet is bounced off at the high hydraulic pressure portion and forms a circulating flow. FIGS. 22 and 23 show an example in which the taper length (ie, H) is set to 1 mm. The calculation result is that the maximum hydraulic pressure is 0.640 MPa, which is lower than that in the case of H = 50 mm, but still higher. (FIG. 22). FIG. 23 shows a state in which a flow in the direction opposite to the running direction of the reinforcing fiber sheet is formed near the constriction.

On the other hand, FIGS. 24 and 25 show the calculation results when H = 0 mm, that is, when there is no portion where the cross-sectional area decreases intermittently in the liquid pool portion. According to this, the maximum hydraulic pressure was 0.166 MPa, which is a calculation result that is considerably lower (about ４) than the case where H = 1 mm. Also, in combination with the low fluid pressure and the absence of the tapered shape near the constricted part, the flow in the direction along the outlet side member near the constricted part becomes large, and the formation of the flow in the direction opposite to the running direction of the reinforcing fiber sheet is reduced. It is suggested that it is weak (FIG. 25).

In order to consider the formation of the circulating flow by the taper length H in more detail, FIG. 26 shows a comparison of FIG. 26 in which the flow velocity when H is changed is colored in gray scale. The flow chart shows that the darker the color, the higher the flow velocity. First, when looking at the diagram showing the flow direction of the liquid, it seems that a circulating flow is formed even at H = 0, but when looking at the flow velocity diagram, once at H = 0 mm, it is once outside the constriction compared with the case of H = 1 mm. , And thereafter, the flow velocity of the liquid flow in the direction opposite to the running direction of the reinforcing fiber sheet is low (lighter in the figure). From this, it is considered that the formation of the circulating flow is considerably weak at H = 0 mm, and the effect of the present invention cannot be obtained. Next, in the case of H = 50 mm, as compared with the case of H = 1 mm, the flow velocity in the direction opposite to the running direction of the reinforcing fiber sheet is larger (darker color) in the direction opposite to the running direction of the reinforcing fiber sheet, not only in the vicinity of the constricted part but also in the place away from it. Are formed, and the effect of the present invention is more enhanced. Furthermore, when H = 0 mm and H = 1 mm, the liquid flow is extremely small at the outer corner (upper right corner in the figure) from the stenosis portion, so that it can be seen that a stagnant portion is formed. When such a stagnant portion is present, the matrix resin, which is a liquid, is likely to be deteriorated. In particular, when a thermosetting resin is used, curing occurs in this portion, and the cured product is carried by the liquid and the process is performed as foreign matter. It may disturb or reduce the quality of the resulting prepreg. However, when the portion where the cross-sectional area decreases intermittently, such as H = 50 mm, is long, such a stagnation portion of the liquid hardly occurs, which is advantageous for stabilizing the process and improving the quality of the prepreg.

As described above, it is shown that the effect of having the portion where the cross-sectional area decreases intermittently, and that the larger the value of H is, the higher the hydraulic pressure and the larger the circulation flow are, and the larger the value of H is. It can be seen that the effect of the present invention can be further enhanced.

Hereinafter, an example of obtaining a prepreg by the prepreg manufacturing method of the present invention will be described. However, the present invention is not construed as being limited to such an example.

<Example 1: Thermosetting wide prepreg (1)>
As the application unit, an application unit of the application unit 20f type shown in FIG. 27 is used, and as a prepreg manufacturing apparatus, a widening device, a smoothing device, and additional impregnation are used from the device having the configuration shown in FIG. A device other than the device can be used.

側壁 The side wall member of the application section can be made of an acrylic resin plate so that the inside can be observed. The direction of travel of the reinforcing fiber sheet in the liquid reservoir is horizontal, and the liquid reservoir has a two-stage taper shape. The first-stage taper has an opening angle of 15 to 20 ° and a taper length (ie, H) of 10 degrees. The opening angle of the second-stage taper can be 5 to 10 °. Further, as the width regulating mechanism, a plate-shaped bush adapted to the inner shape of the application portion as shown in FIG. 8 is provided, and the installation position of the plate-shaped bush can be freely changed so that L2 can be appropriately adjusted. The width U of the stenosis portion can be 300 mm when L2 is 300 mm. The gap D of the stenotic portion is about 0.18 mm, and can be adjusted according to a desired basis weight. In the above case, the aspect ratio of the exit slit is 1500. In order to prevent the matrix resin from leaking from the stenotic portion outlet, the stenotic portion outlet surface can be used with the outside of the bush closed. The distance B defined by the upper surface of the liquid reservoir and the upper surface of the reservoir can be 50 to 70 mm. Further, the length C of the liquid pool portion can be shortened as long as the reinforcing fiber sheet can travel, and specifically, can be set to 100 to 200 mm.

As a reinforcing fiber, a carbon fiber (manufactured by Toray, “Treca (registered trademark)” T800S (24K)) or the like can be used, and a thermosetting epoxy resin composition described later can be used as a matrix resin. Although the number of reinforcing fiber bobbins can be changed according to the basis weight of the prepreg to be produced, a prepreg having a general basis weight can be obtained with 56 yarns.

A biphenol type epoxy resin (“jER (registered trademark) 825” manufactured by Mitsubishi Chemical Corporation) was used as a matrix resin, and the running speed of the reinforcing fiber sheet and the prepreg was reduced to 5 at room temperature (resin viscosity was equivalent to 4 to 7 Pa · s). A prepreg can be produced at a speed of ２５25 m / min.

Further, when the application section is made of a transparent material such as acryl as in this example, the inside of the application section can be observed, so that the running property of the reinforcing fiber sheet can be evaluated. More specifically, the evaluation of the continuous running performance can be performed as follows. That is, the reinforcing fiber sheet is allowed to run continuously for 30 minutes, and a case where there is no fuzz clogging / yarn breakage is “Good”, and a case where the fluff is clogged and yarn breakage is “Bad”. In addition, in order to evaluate the signs of fuzz clogging, the application portion is disassembled after continuous running for 60 minutes and 120 minutes, and the liquid contact surface of the upper surface member is visually observed to check for fuzz. A fuzz attached to the vicinity of the constriction after continuous running is referred to as “poor”, and a portion far from the constriction after continuous running (a boundary between a portion where the cross-sectional area does not decrease and a portion where the cross-sectional area continuously decreases). (Around) is referred to as a fuzz-preventing property “Fair”, and a piece having no fuzz adhering to the liquid contact surface of the upper surface member after continuous running is referred to as “Good”. Further, the vehicle is continuously driven at a running speed of 20 m / min for 60 minutes, and the reinforcing fiber sheet is cracked at the boundary between the portion where the cross-sectional area does not decrease and the portion where the cross-sectional area continuously decreases (the sheet is reinforced in a vertical streak shape). The time during which the fiber runs uniformly without the fiber bundle being torn) or the end of the reinforcing fiber bundle being broken (the part where the reinforcing fiber bundle overlaps) is measured. "Excellent" means that the ratio of the time during which the fiber bundle is running uniformly without cracks and end breaks of the fiber bundle is 90% or more of the total running time, and "Good" means that the ratio is 50% or more and less than 90%. "10% or more and less than 50% is" Fair ", and less than 10% is" Poor ".

では In this example, even if the running speed of the reinforcing fiber sheet is a high-speed running of about 20 m / min, there is no fluff and yarn clogging when H ≧ 30 mm (Good), and the fluff preventing property can be Good. If the relationship L2-W between the width L2 of the lower end of the width regulating mechanism and the width W of the primary prepreg is 0 ≦ L2-W ≦ W + 2 (mm), the cracks in the reinforcing fiber bundle are excelent, and the end of the reinforcing fiber bundle is The break can be set as Excellent.

(4) By appropriately adjusting the tapered shape and the gap D of the constricted portion, the impregnation rate by the peeling method can be made 50% or more. The impregnation rate by the peeling method is as follows: The collected prepreg is sandwiched between adhesive tapes, peeled off, and the reinforcing fiber with matrix resin and the reinforcing fiber without matrix resin are separated. The ratio is calculated from the ratio of the mass of the reinforcing fiber to which the matrix resin adheres to the mass of the reinforcing fiber.

In addition, the basis weight of the primary prepreg thus obtained in the width direction of 100 mm square can be kept within the range of plus or minus 2% by mass for both carbon fiber and resin, and it is possible to obtain excellent uniformity of the basis weight in the width direction. Can be. The basis weight uniformity of the prepreg in the width direction can be evaluated as follows. A prepreg having a width of 300 mm is cut out at the right end, center, and left end in a width of 100 mm in the width direction, and the mass of the prepreg and the mass of the carbon fiber are measured at n = 3. The mass of the carbon fiber is measured as a residue obtained by eluting the resin from the prepreg with a solvent. From this, the average value at each sampling position is calculated, and the average values at each sampling position are compared.

<Example 2: Thermosetting wide prepreg (2)>
The coating section is made of stainless steel, and a plate heater is attached to the outer circumference of the coating section to further heat the matrix resin, so that the temperature and viscosity of the matrix resin can be adjusted while measuring the temperature with a thermocouple. . Other than this, the same application section, prepreg manufacturing apparatus, and reinforcing fiber sheet as those in Example 1 described above can be used.

{Circle around (2)} As the matrix resin, matrix resin A which is a thermosetting epoxy resin composition can be used. This is a mixture of an epoxy resin (a mixture of an aromatic amine type epoxy resin and a bisphenol type epoxy resin), a curing agent (diaminodiphenyl sulfone), and a polyether sulfone, and does not contain polymer particles. The viscosity of the matrix resin A can be measured using ARES-G2 manufactured by TA Instruments, a measurement frequency of 0.5 Hz, a heating rate of 1.5 ° C./min, 50 Pa · s at 75 ° C., 15 Pa · s at 90 ° C., It is 4 Pa · s at 105 ° C. Using this matrix resin A, a prepreg can be prepared by setting the matrix resin temperature of the application section to 75 to 105 ° C. and the running speed of the reinforcing fiber sheet and prepreg to 5 to 25 m / min.

For example, the first-stage taper of the application section has an opening angle of 17 °, the second-stage taper has an opening angle of 7 °, H = 70 mm, L2-W = 0 mm, the matrix resin temperature of the application section is 90 ° C., and the reinforcing fibers When a prepreg is prepared by setting the running speed of the sheet and the prepreg at 20 m / min and the high-speed running property is evaluated, there is no fluff and yarn clogging and the fuzz preventing property can be good. Further, the impregnation degree by the peeling method can be within 50% or more, and the uniformity of the basis weight in the width direction can be within ± 2%.

<Example 3: Thermosetting wide prepreg (3)>
Here, an example of simple additional impregnation and subsequent resin film lamination will be described. The application section is the same as in Example 2, and the prepreg manufacturing apparatus shown in FIG. 28 can be used.

強化 The reinforcing fiber sheet described in Example 2 is coated with the matrix resin A also described in Example 2 at 80 to 100 ° C. to obtain a primary prepreg. Then, additional impregnation is performed by an additional impregnation device installed immediately after the coating section, and the degree of impregnation can be increased so that the impregnation rate based on the water absorption rate becomes 3 to 15%. At this time, the simple additional impregnation device can be a multi-stage nip roll, and a release sheet can be inserted on the nip roll. The release sheet can be run on a circuit. The impregnation ratio based on the water absorption is calculated from the mass change when a prepreg is cut into 10 cm × 10 cm, one side of which is 5 mm, and immersed in water for 5 minutes according to the method described in JP-T-2016-510077. it can. Thereafter, the resin film is laminated on the prepreg having a high degree of impregnation from above and below or from one side, and this is guided to an additional impregnator to adjust the impregnation rate to 0.1 to 15%. The running speed of the reinforcing fiber sheet or prepreg can be 5 to 25 m / min.

For example, the first-stage taper of the application section has an opening angle of 17 °, the second-stage taper has an opening angle of 7 °, H = 70 mm, L2-W = 0 mm, and the temperature of the matrix resin A of the application section is 90 ° C. A prepreg is prepared by setting the surface temperature of the nip roll of the simple additional impregnating device to 100 ° C., using a laminated body of a matrix resin B film described later and a release sheet as a resin film, and setting the traveling speed of the reinforcing fiber sheet and the prepreg to 20 m / min. Then, the impregnation rate based on the water absorption rate can be set to about 5%. The matrix resin B is a thermosetting epoxy resin composition, and a mixture of an epoxy resin (a mixture of an aromatic amine type epoxy resin and a bisphenol type epoxy resin), a curing agent (diaminodiphenyl sulfone), a polyether sulfone, and a polymer. As the particles, those obtained by adding “particle 3” (Tg = 150 ° C.) described in Examples of Japanese Patent Application Laid-Open No. 2011-162609 to 13% by mass when the total mass of the resin composition is 100% by mass are used. The viscosity thereof was 118 Pa · s at 75 ° C., 32 Pa · s at 90 ° C., and 10 Pa · s at 105 ° C. when measured at a measurement frequency of 0.5 Hz and a heating rate of 1.5 ° C./min. This matrix resin B can be used as a resin film by a known method.

Six layers of this polymer particle-containing prepreg are laminated and cured for 2 hours at 180 ° C. and 6 kgf / cm ² (0.588 MPa) using an autoclave to obtain CFRP. The tensile strength can be about 3.0 GPa, which is a mechanical property suitable as a structural material for aerospace. The CFRP tensile strength is measured in the same manner as in WO2011 / 118106 pamphlet, and a value obtained by standardizing the volume% of the reinforcing fibers in the prepreg to 56.5% can be used. The cross section of the obtained CFRP is such that the reinforcing fiber layers are orderly laminated in the horizontal direction, a matrix resin layer is formed between the reinforcing fiber layers, and polymer particles are further provided between the reinforcing fiber layers. Most of can be arranged. This state can be confirmed by CFRP cross-sectional observation using an electron microscope or the like.

The tensile strength of CFRP obtained by curing a prepreg prepared by a conventional hot melt method using carbon fiber and matrix resin A at 180 ° C. and 6 kgf / cm ² (0.588 MPa) for 2 hours using an autoclave is 2. It is about 9 GPa.

<Example 4: Thermoplastic prepreg tape (1)>
When using the application section 20g shown in FIG. 29, the initial impregnation is performed by passing a plurality of reinforcing fiber sheets through a plurality of direction changing members provided in the liquid pool section, and after laminating / unifying, further narrowing is performed. In addition to measuring and impregnating the matrix resin applied in the section, the prepreg cross-sectional shape can be shaped. When a matrix resin mainly composed of a thermoplastic resin, particularly a super engineering plastic having high heat resistance, is used, a particularly high-temperature process is required for the impregnation. Therefore, in order to reduce the load in the additional impregnation, it is effective to advance the impregnation in the application section, and the application section as shown in FIG. 29 can be cited as a preferable example. Further, in order to suppress thermal decomposition and oxidative decomposition, it is preferable to fill the inside of the application section with an inert gas such as nitrogen or argon. For this reason, it is preferable to provide a seal member in the opening within a range that does not hinder the running of the reinforcing fiber sheet.

In producing the thermoplastic prepreg tape, the coating portion 20g shown in FIG. 29 has an opening angle of 15 to 20 ° for the first-stage taper, an opening angle of 5 to 10 ° for the second-stage taper, and H = 50 to 70 mm. L2-W = 0-1 mm, B = 30-70 mm, C = 250-350 mm, the application section is filled with nitrogen, and a degassing mechanism can be used. As the prepreg manufacturing apparatus, the apparatus shown in FIG. 23 can be used. In FIG. 30, one reinforcing fiber sheet is formed by arranging three reinforcing fibers, and two sheets are used to produce a prepreg. However, the number of reinforcing fiber bobbins and the number of reinforcing fiber sheets are shown. Can of course be changed as appropriate. For example, as a reinforcing fiber, a carbon fiber (manufactured by Toray, "Treca (registered trademark)" T800S (24K)) is used, and a single reinforcing fiber sheet is formed with three yarns, and two sheets of the reinforcing fiber sheet are used. A prepreg having a width of 20 mm is manufactured. In addition, a prepreg is manufactured by using low-viscosity polyamide 6 as the matrix resin and setting the temperature of the matrix resin in the application section to 280 to 300 ° C. At this time, as shown in FIG. A nip roll is provided, and the surface temperature of the nip roll is set to 200 to 250 ° C. to completely perform the impregnation. The running speed of the reinforcing fiber sheet or prepreg can be 5 to 20 m / min. The molded article of the thermoplastic prepreg obtained in this way has no voids inside and can exhibit good mechanical properties. In the apparatus shown in FIG. 30, a calender roll and a traction apparatus can be arranged downstream of the simple additional impregnation apparatus, for example, as described in Patent Document 3.

<Example 5: Thermoplastic prepreg tape (2)>
In Example 4 described above, the matrix resin can be changed to super engineering plastic. For example, when PEEK is used, the temperature of the matrix resin in the application section is 350 to 420 ° C., and the surface of the nip roll for easy additional impregnation is used. Complete impregnation can be performed at a temperature of 300 to 400 ° C. When PEKK is used, complete impregnation can be performed by setting the temperature of the matrix resin in the application section to 380 to 420 ° C. and the surface temperature of the nip roll for easy additional impregnation to 320 to 420 ° C. The running speed of the reinforcing fiber sheet or prepreg can be 5 to 20 m / min. The molded article of the thermoplastic prepreg obtained in this way has no voids inside and can exhibit good mechanical properties and heat resistance.

<Prepreg manufacturing equipment>
As a prepreg manufacturing apparatus, an apparatus having a configuration shown in FIG. 31 (resin supply section is omitted in drawing) was used.

<Coating part>
As the coating unit, a coating unit of the coating unit 20h type shown in FIG. 32 was used, and side members of the coating unit were made of an acrylic resin plate so that the inside state could be observed. However, only the constriction was made of stainless steel. In addition, the running direction of the reinforcing fiber sheet in the portion where the cross-sectional area decreases along the running direction of the reinforcing fiber sheet in the liquid pool is horizontal (0 °), the configuration of the liquid pool is a two-stage tapered shape, The opening angle of the first-stage taper was 17 °, and the opening angle of the second-stage taper was 7 °. Further, as a width regulating mechanism, a plate-shaped bush adapted to the inner shape of the application section as shown in FIG. 8 was provided, and L2 was set to 20 mm. The gap D at the stenosis was 0.18 mm. In addition, the outside of the stenosis portion was closed off from the bush so that the matrix resin did not leak from the stenosis portion exit. The distance B between the lower surface of the upper surface member constituting the application unit and the upper surface of the storage unit was 30 mm. The horizontal length C of the liquid reservoir was 120 mm. In addition, the installation position of the direction changing member for adjusting the running direction of the reinforcing fiber sheet in the application section was located on the upstream side of the portion of the liquid reservoir where the cross-sectional area continuously decreases.

<Reinforced fiber sheet>
For the preparation of the prepreg, three yarns of carbon fiber (manufactured by Toray, "Treca (registered trademark)" T800S (24K)) were used as reinforcing fibers.

<Matrix resin>
A biphenol-type epoxy resin ("jER (registered trademark)" 825, manufactured by Mitsubishi Chemical Corporation) was used as the matrix resin. The resin viscosity at room temperature is 4 to 7 Pa · s (catalog value).

<Prepreg manufacturing process>
The reinforcing fibers were pulled out from the reinforcing fiber bobbin hung on the creel, and three reinforcing fiber yarns were arranged in the width direction by a reinforcing fiber arranging device, and a reinforcing fiber sheet was formed. . Thereafter, the prepreg was pulled out from the application section, a release sheet was provided from above and below, and then wound up. The running speed of the reinforcing fiber sheet and the prepreg was set to 20 m / min.

<Evaluation of continuous running performance>
In order to evaluate the continuous running property in the application section of the reinforcing fiber sheet, the running was continuously performed for 30 minutes, and those having no fuzz clogging and thread break were designated as "Good", and those having fuzz clogged and thread broken were designated as "Bad".

Also, in order to evaluate the signs of fuzz clogging, the coating portion was disassembled after continuous running for 60 minutes and 120 minutes, and the liquid contact surface of the wall member was visually observed to check for the presence of fuzz. The fuzz-preventing property "Poor" is applied to the portion having fluff near the stenosis portion after continuous running, and the portion far from the stenosis portion 23 after continuous running (the portion where the cross-sectional area does not decrease and the portion where the cross-sectional area decreases continuously) Those with fuzz attached to the vicinity of the boundary) were evaluated as “fair prevention”, and those without fuzz on the liquid contact surface of the upper surface member after continuous running were evaluated as “good” to evaluate fuzz prevention. did.

Further, the fiber was continuously run at a running speed of 20 m / min for 60 minutes, and the fiber bundle was broken (a portion where the sheet-like carbon fiber bundle was torn in a vertical streak) or the end of the fiber bundle was broken in the reinforcing fiber sheet immediately above the liquid pool. The time during which there was no (the portion where the carbon fiber bundles overlapped) running uniformly was measured. "Excellent" means that the ratio of the time during which the fiber bundle is running uniformly without cracks and end breaks of the fiber bundle is 90% or more of the total running time, and "Good" means that the ratio is 50% or more and less than 90%. "10% or more and less than 50% were designated as" Fair ", and those less than 10% were designated as" Poor ".

<Evaluation of impregnation degree (peeling method)>
The collected prepreg was sandwiched between adhesive tapes and peeled off to separate the reinforcing fibers to which the matrix resin had adhered and the reinforcing fibers to which the matrix resin had not adhered. Then, the ratio of the mass of the reinforcing fibers to which the matrix resin adhered to the total mass of the loaded reinforcing fiber sheet was determined by a peeling method, and was defined as the matrix resin impregnation rate.

[Examples 1 to 3]
The values of the taper length (ie, H) and L2-W were changed as shown in Table 1, and prepregs were produced. From this, it can be seen that the longer the H, the better the fuzz prevention properties, and the smaller the value of L2-W, the less likely it is for the reinforcing fiber sheet to crack or break at the end.

Further, the impregnation rate by the peeling method was 50 to 60% in each case, and it was found that the impregnation was progressing in the application part.

[Comparative Example 1]
As shown in Table 1, when a value of L2-W was set to 12 mm and a prepreg was produced, cracks in the reinforcing fiber sheet and cracks at the ends occurred.

[Comparative Example 2]
A prepreg was prepared in the same manner as in Example 1 under the conditions shown in Table 1 using a coating portion having no portion where the cross-sectional area was continuously reduced (H = 0), but running started at 20 m / min. Later, the reinforcing fiber sheet was immediately clogged, and the continuous running property was poor.

[Example 4]
Reinforcing fibers were drawn from the reinforcing fiber bobbin hung on the creel, and three reinforcing fiber yarns were arranged in the thickness direction by a reinforcing fiber arrangement device, and a prepreg was produced in the same manner as in Example 1 (L2-W = 0). . At this time, L2 was set to 7 mm. In addition, the gap D of the constricted portion was set to 0.5 mm. As a result of the evaluation of the running property, the continuous running property and the anti-fuzz property (60 minutes, 120 minutes) were all Good, and both the cracks and the end breaks of the reinforcing fiber sheet were Excellent.

The prepreg obtained by the production method of the present invention is a FRP typified by CFRP, and is a structural material or interior material for aerospace applications, automobiles, trains, ships, etc., a pressure vessel, an industrial material application, a sports material application, a medical device. It can be widely used for applications, housing applications, civil engineering and construction applications.

1a Reinforcing fiber 1b Reinforcing fiber sheet 1c Primary prepreg 1d Prepreg 2 Matrix resin 3 Release sheet 4 Resin film 11 Creel 12 Reinforcing fiber bobbin 13 Arrangement device 14, 15 Transport rolls 16a, 16b Supply device 17 Winder 20 Coating part 21, 21a 21b Wall member 22 Liquid reservoir 22a Portion of liquid reservoir where cross-sectional area does not decrease 22b Portion of liquid reservoir where cross-sectional area decreases continuously 22c Portion of liquid reservoir where cross-sectional area decreases intermittently 23 narrowed portion 24 upper surface member 25 lower surface member 26 deaeration mechanism 27 side member 28 outlet 29 outlet side member 30 opening 31 direction changing member 32 side wall member 33 gaps 34, 34a, 34b between reinforcing fiber sheet 1b and side wall member 32 Mechanism 40 Application part 41 of another embodiment different from the present invention Liquid reservoir 42 Boundary 43 Reservoir 44 Liquid level 45 Seal member 100 Coating device B Distance C defined by upper surface of liquid reservoir 22 and upper surface of reservoir 43 Length of liquid reservoir D Dap G Position at which width is regulated H Liquid The length L of the portion 22b of the pool portion where the cross-sectional area continuously decreases The width R of the liquid pool portion 22, Ra, Rb The vortex flow T The circulating flow U The width W of the constriction portion 23 Width X of the next prepreg 1c Direction perpendicular to the running direction YX, Z of the reinforcing fiber sheet Z Vertical downward direction θ Opening angle of the tapered portion 411 Creel 412 Reinforcing fiber bobbin 413 Direction changing guide 414 Reinforcing fiber 415 Reinforcing fiber arrangement device 416 Reinforcing fiber Sheet 417 Widening device 418 Smoothing device 419 Conveyance roll 420 Reinforced fiber sheet preheating device 430 Coating section 431 First coating section 432 Second coating section 44 Supply device (above)
443 Feeder (bottom)
444 High tension take-up device 445 Direction changing roll 446 Resin film or release sheet 447 Laminating roll 450 Additional impregnating device 451 Hot plate 452 Heating nip roll 453 Simple additional impregnating device 454 Heating nip roll 455 Heating S-shaped roll 456 Contact roll 461 Cooling device 462 Take-up device 463 Release sheet (upper) winding device 464 Winder 471 Primary prepreg 472 Pre-preg / release sheet (sheet-like integrated material)

Claims

Inside the application section where the matrix resin is stored, a reinforcing fiber sheet is
A method for producing a prepreg including a step of applying a matrix resin to a reinforcing fiber sheet by passing in a horizontal direction or an inclined direction,
The coating unit includes a liquid reservoir and a constricted portion communicated with each other,
The liquid reservoir has a portion whose cross-sectional area is continuously reduced along the running direction of the reinforcing fiber sheet,
The constricted portion has a slit-shaped cross-section and has a cross-sectional area smaller than the maximum cross-sectional area of the liquid pool portion, and the width L of the terminal end of the liquid pool portion and the sheet-like reinforcing fiber bundle at the outlet of the constricted portion. Satisfies the relationship of the following equation (1):
Method for producing prepreg.
L ≦ W + 10 (mm) (1)
The method for producing a prepreg according to claim 1, wherein the length in the running direction of the portion where the cross-sectional area in the liquid reservoir is continuously reduced is 10 mm or more.
方法 The method for producing a prepreg according to claim 1 or 2, wherein the width of the reinforcing fiber sheet is regulated in the liquid reservoir.
(4) The method for producing a prepreg according to any one of (1) to (3), wherein additional impregnation is performed on the primary prepreg drawn out from the application section.
The method for producing a prepreg according to any one of claims 1 to 3, wherein a resin film is provided on at least one surface of the primary prepreg pulled out from the application section.
The method for producing a prepreg according to claim 4, wherein a resin film is provided on at least one surface of the prepreg after the additional impregnation.
A coating device for applying a matrix resin to the reinforcing fiber sheet,
A traveling mechanism for traveling the reinforcing fiber sheet in a horizontal direction or an inclined direction,
It has an application part, the application part is capable of storing a matrix resin therein, and further includes a liquid reservoir part and a constricted part that are communicated with each other,
The liquid reservoir has a portion whose cross-sectional area is continuously reduced along the running direction of the reinforcing fiber sheet,
The coating device, wherein the constricted portion has a slit-shaped cross-section and has a cross-sectional area smaller than the maximum cross-sectional area of the liquid reservoir.
The coating device according to claim 7, further comprising an opening at an upper portion of the coating portion for allowing the reinforcing fiber sheet to pass therethrough.
A gantry for mounting a reinforcing fiber or a reinforcing fiber fabric, the coating apparatus according to claim 7 or 8, and a prepreg manufacturing apparatus including a winder for winding the prepreg.